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The Chemistry of 1,1,2,2,9,9,10,10-Octafluoro[2.2] Paracyclophanes

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PAGE 1

THE CHEMISTRY OF 1,1,2,2,9,9,10,10-OCTAFLUORO[2.2] PARACYCLOPHANES By YIAN ZHAI A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLOR IDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2005

PAGE 2

Copyright 2005 by Yian Zhai

PAGE 3

The work presented in this dissertati on is dedicated to my wife Lazhen.

PAGE 4

ACKNOWLEDGMENTS I would like to thank my advisor and the chair of my committee, Dr. William R. Dolbier, Jr., for affording me the opportunity to study in his laboratory. The time spent under his direction has been invaluable, and I am indebted to him for his patience, guidance, and encouragement. With as much owed respect and thanks, the friendship and mentoring of Dr. Merle A. Battiste will not be forgotten as well as his insight and inspiration on my research. Without Dr. Ion Ghivirigas help in NMR characterizations, I would have had serious problems in identifying compounds; I also thank Dr. Merle A. Battiste, Dr. Ion Ghiviriga, Dr. Weihong Tan, and Dr. John Sabin for being on my committee and for their time and effort. I acknowledge Dr. Khalil Abboud for the x-ray analysis with great appreciation. Personally, I would also like to thank my wife La-Zhen Xiang. Without her love and support, I would not be in this position today. I also thank my family: mother Feng-Xian Zhang, father Jian-Ting Zhai, my sister Xiao-Chun Zhai, Xiao-Yan Zhai, my mother-in-law Qin-Ju Tang, and father-in-law Li-Wang Xiang. Their support and love are acknowledged, and I thank them for that. Over the years I have been taught by some truly inspirational teachers, I extend my thanks to Dr. Wei-Jue Ding for her mentoring and for opening the door into the realm of organic chemistry. I wish to thank past and present members of the Dolbier group for their friendship and help. I also want to take a moment to specifically thank Dr. Jian-Xin Duan for his friendship and help in everything. I would also like to give specific thanks to iv

PAGE 5

Dr. David Powell, and the MS group as well as the CHN group for their technical support with my MS characterization elemental analysis. Dr. Kirk S. Schanzes group provided the UV and fluorescence instruments for some of my compounds. Dr. Yao Liu helped me in the fluorescence spectra characterization. Finally, I appreciate everything that the Chemistry Department has done during my time here. v

PAGE 6

TABLE OF CONTENTS page ACKNOWLEDGMENTS ..................................................................................................iv LIST OF TABLES ............................................................................................................ viii LIST OF FIGURES .............................................................................................................x ABSTRACT ..................................................................................................................... xiv CHAPTER 1 INTRODUCTION ......................................................................................................1 1.1 A Brief History of Cyclophane Chemistry .....................................................1 1.1.1 [2.2] Paracyclophane ........................................................................3 1.1.2 Other Cyclophanes ...........................................................................5 1.2 The Physical and Chemical Properties of Cyclophanes ...............................10 1.3 1, 1, 2, 2, 9, 9, 10, 10-Octafluoro[2.2]paracyclophane (AF4) .....................14 1.4 Aryne Chemistry ...........................................................................................17 2 4,5-DEHYDROAND 4,5,15,16-BIS-DEHYDROOCTAFLUORO[2.2]PARACYCLOPHANES: FACILE GENERATION AND EXTRAORDINARY DIELS-ALDER REACTIVITY .......24 2.1 Introduction ...................................................................................................24 2.2 Results and Discussions ................................................................................26 2.2.1 Synthesis of Aryne Precursors .......................................................26 2.2.2 Reactions of 4, 5-Dehydrooctafluoro[2.2]paracyclophane, 1........27 2.2.3 Reactions of 4,5,15,16-Bis-(Dehydro)octafluoro[2.2]paracyclophane, 17 ...............35 2.2.4 NMR Discussion. 100 .......................................................................36 2.2.5 X-ray Discussion. ...........................................................................38 2.3 Conclusion ....................................................................................................40 2.4 Experimental .................................................................................................41 3 CADOGAN METHOD AND REACTION MECHANISM ...................................55 3.1 Introduction ...................................................................................................55 3.2 Results and Discussion .................................................................................56 3.2.1 The Cadogan Method .....................................................................56 3.2.2 Ene Reactions .................................................................................57 vi

PAGE 7

3.2.3 2-Methoxynaphthalene Reaction ...................................................60 3.2.4 Tetracyclone Reaction ...................................................................61 3.2.5 Norbornadiene Reactions ...............................................................62 3.2.6 Reaction with 1,3,5-Cycloheptatriene ............................................63 3.3 Mechanistic Study of AF4-yne .....................................................................69 3.3.1 Base and Solvent Study .................................................................70 3.3.2 The Different Selectivity of the Two Methods ..............................71 3.3.3 The Selectivity of AF4-yne Toward Diels-Alder and Ene reaction ...................................................................74 3.3.4 t-Butoxide Ion Adduct ...................................................................76 3.3.5 Mechanism .....................................................................................77 3.3.6 Isotopic Labeling Experiments ......................................................82 3.3.7 Reactions in the Presence of Electron Trap Reagents...................83 3.4 Conclusion ....................................................................................................85 3.5 Experimental .................................................................................................87 4 EFFICIENT SYNTHESES OF NOVEL NAPHTHALENOAND ANTHRACENO-OCTAFLUORO[2.2]PARACYCLOPHANES ...........................99 4.1 Introduction ...................................................................................................99 4.2 Results and Discussion ...............................................................................103 4.3 UV and Fluorescence Spectrum ..................................................................109 4.4 Conclusion ..................................................................................................116 4.5 Experimental ...............................................................................................117 5 NOVEL CAGE COMPOUND ...............................................................................121 5.1 Introduction .................................................................................................121 5.2 Result and Discussions ...............................................................................124 5.2.1 Synthesis of Cage Compound ......................................................124 5.2.2 Cage with Triplet Oxygen ............................................................130 5.2.3 Cage with Chlorine ......................................................................131 5.2.4 Cage with Singlet Oxygen ...........................................................132 5.2.5 Cage with Bromine ......................................................................134 5.3 Conclusion ..................................................................................................135 5.4 Experimental ...............................................................................................135 X-RAY DATA .................................................................................................................142 LIST OF REFERENCES .................................................................................................158 BIOGRAPHICAL SKETCH ...........................................................................................174 vii

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LIST OF TABLES Table page 1-1 Structural features of AF4 and [2.2]paracyclophane 11 ...............................................15 2-1. Diels-Alder reactions from treatment of 4-iodooctafluoro[2.2] paracyclophane, 1, with potassium t-butoxide. ........................................................30 2-2. Diels-Alder reactions from treatment of 4, 15-diodo-octafluoro [2.2]paracyclophane, 18, with potassium t-butoxide, in refluxing solvent. ................................................36 3-1 [2+2+2] to [2+2] products ratio of norbornadiene with AF4-yne ..............................63 3-2 Base and solvent effects in AF4-yne reaction with anthracene ..................................70 3-3 Base solubility in butyl ether solvent .........................................................................71 3-4 Competition reactions of naphthalene to benzene ......................................................72 3-5 Selectivity in Diels-Alder reaction under Cram conditions ........................................73 3-6 Competition reactions of benzene to 1-octene ...........................................................74 3-7 Competition reaction of anthracene with 1-octene in butyl ether for 5 hours at 110under Cram condition ...............................................................................74 3-8 Reaction of AF4-yne with olefins in butyl ether ........................................................75 3-9 The AF4-yne selectivity of DA over Ene reaction under Cadogan conditions (3 h at 110 in butyl ether) .....................................................................................75 3-10 Summary of t-butoxide adduct under Crams conditions .........................................77 3-11 Ionization potential of alkenes 126 ..............................................................................78 3-12 IAF4 reduced to AF4 in refluxing butyl ether a .........................................................83 3-13 Additive effect on the reduction of AF4-yne with 1-octene under Cram conditions at 110 for 3 h ........................................................................................................84 3-14 Additive effect on the reaction of AF4-yne with anthracene under Cram conditions at 110 for 3 h ........................................................................................................85 viii

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4-1 Fluorescence spectra data of fluorinated [2.2]paracyclophanes ...............................116 5-1 Base screening results ...............................................................................................126 5-2 Solvent effect in the reaction of pseudo-ortho-diIAF4 with anthracene under microwave conditions ..................................................................................127 ix

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LIST OF FIGURES Figure page 1-1 [2.2](1,3)Cyclophane .....................................................................................................1 1-2 [2.2](1,4)Cyclophane .....................................................................................................1 1-3 Chemical shift ( 1 H NMR) and charge transfer complex of [2.2] paracyclophane ........3 1-4 Geometry of [2, 2] paracyclophane 11 ............................................................................4 1-5 Different bridge connection of [2.2]cyclophane ............................................................4 1-6 Chemical vapor deposition (CVD) polymerization .......................................................5 1-7 Effect on aromatic protons .........................................................................................6 1-8 Distances of two aromatic protons to the other benzene deck ......................................7 1-9 Synthesis of [2.2][1,4]naphthalenoparacyclophane .......................................................7 1-10 Synthesis of [2.2](1,4)naphthalenophane ....................................................................8 1-11 [2.2]Anthracenophane and [2.2](2,5)heterophanes .....................................................8 1-12 [2.2](1,4)Athracenophane ............................................................................................9 1-13 Highly condensed phanes ..........................................................................................10 1-14 Photo reaction of [2.2]naphthalenopahane ................................................................12 1-15 Photo and thermal reversibility of [2.2](1,4)anthracenophane ..................................13 1-16 Octafluoro[2.2]paracyclophane (AF4 ) .....................................................................15 1-17 Nitration and dinitration of AF4 ................................................................................16 1-18 Generation of benzofuran aryne ................................................................................17 1-19 C 14 Labelling experiment ...........................................................................................18 1-20 Methods of benzyne generation .................................................................................18 1-21 Aryne with furan ........................................................................................................19 x

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1-22 Co-cyclisation of arynes with alkynes to phenanthrene derivatives ..........................20 1-23 Palladium catalyzed reactions of allyl chlorides with benzyne .................................20 1-24 Palladium catalyzed reaction between allytributylstannane, allyl chloride, and benzyne .....................................................................................................................21 1-25 Paracyclophane aryne ................................................................................................22 1-26 [2.2]Paracyclophane bis-aryne ..................................................................................22 2-1 Bis-paracyclophane aryne with furan reaction ............................................................25 2-2 Monoand bis-AF4-yne ..............................................................................................26 2-4 Diels-Alder reaction of AF4-yne .................................................................................29 2-5 Products of 1,4-dimethylnaphthalene and 2,3-dimethylnaphthalene ..........................31 2-6 Products of 2-methoxylnaphthalene with AF4-yne .....................................................32 2-7 Products of furan and 2,5-diphenylfuran with AF4-yne ..............................................33 2-8 Product of [2.2]paracyclophane with AF4-yne (bold shifts on this structure indicate protons pointed toward the viewer) ............................................................34 2-9 Products of bicyclo[2.2.1]hepta-2,5-diene with AF4-yne ...........................................35 2-10 The bis-Diels-Alder reaction of AF4-yne ..................................................................37 2-11 ORTEP drawing of anthracene adduct 5 and endo furan adduct 12a ........................39 2-12 ORTEP drawing of [2.2]paracyclophane adduct 14 and bis naphthalene adduct 20 ..................................................................................................................39 3-1 Decomposition of benzene-diazonium slat ..................................................................55 3-2 1-Octene with AF4-yne reaction .................................................................................57 3-3 Chemical shifts of cyclopentene and cyclohexene products .......................................58 3-4 Chemical shifts of products from the reaction of -methylstyrene with AF4-yne ......60 3-5 Retro Diels-Alder reaction of 2-methoxynaphthalene adduct to phenyl anthraceno[2.2] paracyclophane .........................................................................................................61 3-6 Chemical shifts of tetracyclone with AF4-yne product ...............................................61 3-7 Chemical shifts of cycloheptatriene products 8 and 9 .................................................65 xi

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3-8 Primary AF4-yne ene product with AF4-yne reaction to products 8a&8b .................68 3-9 S RN 1 reduction of IAF4 to AF4 ...................................................................................80 3-10 Reduction mechanism of IAF to AF4 in the presence of olefin ................................81 3-11 Olefin with KO t Bu complex ......................................................................................82 4-1 Anthracenophane 1 and naphthalenophane 2 ............................................................100 4-2 [2.2](1,4)(9,10)anthracenophane 3, [2.2] paracyclo(9,10) anthracenophane 4 and [2.2](1,4)naphthaleno(9,10)anthracenophane ........................................................100 4-3 Polyfluoroaryl [2.2]cyclophanes 6 and 7 ...................................................................101 4-4 Diles-Alder reaction of mono and bis-AF4-yne ........................................................102 4-5 Bridge fluorinated [2.2]cyclophane 12, 13, 14 and 15 ..............................................103 4-6 Reaction of adduct with 3,6-dipyridinyl-1,2,4,5-tetrazine 16 ...................................104 4-7 Fragment of [2.2]cyclophane 12 ................................................................................105 4-8 Chemical shifts of [2.2]cyclophane 12, 13, 14 and 15 ..............................................106 4-9 Dimerization of phenyl anthracenophane 21 .............................................................108 4-10 ORTEP drawing of compound 21 ...........................................................................108 4-11 UV spectra of bridge fluorinated [2.2]cyclophanes 12-15 ......................................110 4-12 Fluorescence spectra of bridge fluorinated [2.2]cyclophane ...................................111 4-13 UV spectra in dichloromethane of compound 21 and 22 compared to compound 12 and 13. .............................................................................................113 4-14 Fluorescence spectra in dichloromethane of compound 21 and 22 .........................114 4-15 Fluoresence of Diels-Alder products in dichloromethane .......................................115 5-1 Pyramidalized alkene .................................................................................................122 5-2 Some pyramidalized alkenes .....................................................................................123 5-3 Tribenzo-4,7-dihydroacepentalene derivative ...........................................................123 5-4 4,5,15,16-bis(dehydrooctafluoro[2.2]paracyclophane 4 and 4,5,12,13-bis(dehydrooctafluoro[2.2]paracyclophane 5 .........................................................124 xii

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5-5 The reaction of the pseudo-ortho-4,12-diiodooctafluoro[2.2]paracyclophane with anthracene ...............................................................................................................124 5-6 NMR assignments of pseudo-ortho-diiodoAF4 with anthracene products under Cram conditions .....................................................................................................125 5-7 ORTEP drawing of the cage compound (right) and epoxide (left) ...........................129 5-8 Tricycle[3.3.2.0 3,7 ]-dec-3(7)-ene 10 and dodecahedradiene 11 ................................130 5-9 Cage compound reaction with oxygen ......................................................................130 5-10 Syn-sesquinorbornene ..............................................................................................131 5-11 Bubbling oxygen through the solution of cage compound ......................................132 5-12 Trapping the intermediate of the reaction of singlet oxygen with pyramidalized alkene .....................................................................................................................133 5-13 Compound 14 and cage with singlet oxygen product 15 .........................................134 5-14 Reaction of cage with bromine ................................................................................135 xiii

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Abstract of Dissertation Pres ented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy THE CHEMISTRY OF 1,1,2,2,9,9,10,10-OCTAFLUORO[2.2] PARACYCLOPHANES By Yi-An Zhai May 2005 Chair: William R. Dolbier, Jr. Major Department: Chemistry The chemistry of [2.2]cyclophanes has a number of unique and interesting theoretical and practical aspects that have attracted the interests of organic chemists for more than 50 years. It has been demonstrated in earlier work from our lab that the chemistry of 1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane differs significantly form that of its non fluorinated analogs. The initial research in the current project involved the discovery of two good methods for the generation of 4,5-dehydro and 4,5,15,16bis(dehydro)-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane-yne (AF4-yne and bis-AF4-yne) chemistry. The AF4-yne generated from the reaction of potassium t-butoxide with iodo AF4 derivatives gave very high yields for Diels-Alder (DA) reactions, including the very poor DA substrate, benzene. Bis-AF4-yne also gave high yields for DA reactions. A new synthetic method of synthesizing new bridge fluorinated polynuclear paracyclophanes has been developed by xiv

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using these DA adducts as intermediates. The physical and chemical properties of those new paracyclophanes were investigated. When AF4 aryne is generated from the nitrosyl acetamide AF4 derivative, it has a very different reactivity towards alkene substrates compared to that generated from IAF4 via the KO t Bu method. Experiments including isotopic labelling reactions were carried out to gain an understanding of the differences observed for the two methods. A novel cage compound was discovered by the reaction of pseudo-ortho-diiodo-AF4 with KO t Bu and anthracene. The physical and chemical properties of this cage compound were investigated. Finally, a study of the reduction of AF4-yne to AF4 was carried out, and it was found that electron acceptor reagents have an effect on the reduction rate of IAF4 to AF4. This process might involve electron transfer (ET) to produce radical anion as reaction intermediate. The selectivity of AF4-yne toward DA reaction under different reaction conditions was established, and it was found that the DA reaction of anthracene with AF4-yne is 2.7*10 4 times faster than the same reaction with benzene. xv

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CHAPTER 1 INTRODUCTION 1.1 A Brief History of Cyclophane Chemistry Cyclophane chemistry has been studied for more than one century and has been broadened dramatically. Cyclophane chemistry has both theoretical and practical use and plays an important role in the study of electronic interactions and system strain. It demonstrates that two or more closely placed electron clouds have both steric and electronic interactions. Transannular interactions also play an important role in the stabilization of the cations and anions generated from cyclophanes. The first cyclophane was synthesized by Pellegrin 1 in 1899 through Wurtz coupling of 1,3-bis(bromomethyl)benzene (Figure 1-1). CH2Br Na 2CH2Br Figure 1-1 [2.2](1,3)Cyclophane Brown and Farthing synthesized [2.2] paracyclophane in 1949 by pyrolysis of p-xylene (Figure 1-2), and published a low resolution X-ray structure analysis. 2, 3 German chemists Lttringhaus 4 and Huisgen 5 first reported the synthesis of alphatic bridged cyclophanes. Figure 1-2 [2.2](1,4)Cyclophane 1

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2 These studies illustrated that the aromatic rings in cylcophanes are not planar but distorted out of planarity by bending. The x-ray study unequivocally revealed that a benzene ring can be distorted into boat-, chair-, and twist-forms by clamping or bridging them in cyclophanes. These aberrations led to unusual spectroscopic properties and chemical reactivities. The interaction in the [2.2]paracyclophane between the two benzene rings leads to a novel extended -electron system. The Highest Occupied Molecular Orbital (HOMO) is higher than that of the corresponding alkyl benzene; the Lowest Unoccupied Molecular Orbital (LUMO) is lower than that in the open chain molecule. Thus, the energy gap between the HOMO/LUMO is much lower than the open chain compounds. The same type of interaction, albeit weaker, exists in the [3.3]cyclophane but is absent in the more widely separated [4.4]cyclophane, where the individual benzenes behave as separated -electron systems. Cyclophane chemistry gives an opportunity to increase the distortion gradually and successively, which changes the chemical and spectroscopic properties of the aromatic units. Some interesting functionized units can be placed very close to the aromatic ring. For example, one can compare the transannular electronic effects and steric strain of multi-layered cyclophanes or heterocyclophanes with these in the parent hydrocarbon compounds. 6 Cyclophane chemistry also has found applications. Cyclophane may serve as a building unit for nests, hollow cavities, multi-floor structures, helices, macro-polycyclics, macro-hollow tubes, novel ligand systems, etc. Cyclophane chemistry also has importance in supermolecular chemistry, molecular recognition, and may be used as a building block for organic catalysts (novel ligand) and crown ethers. 6-8

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3 How far can aromatic rings be distorted? What are the physical and chemical properties of these cyclophanes? These questions have been pursued for decades. The chemistry of uniquely strained [2.2]paracyclophane and other cyclophanes has been the subject of research since Crams first description of [2.2]paracyclophanes. 9 Since then, numerous publications have emerged. Many different cyclophanes such as meta, para and heterocyclophanes have been synthesized and studied. 1.1.1 [2.2] Paracyclophane The [2.2] paracyclophane is a special example and reflects the essence of cyclophane chemistry. Its two aromatic rings are placed face to face and have a chair-like configuration instead of planar (deformation of the benzene ring), due to the -electron interaction between the two aromatic rings. Chemists are also interested in the transannular electronic effects on the chemical reactivities of the ring and bridge. Their reactivity is induced by the other ring and also causes a charge transfer interaction (Figure 1-3) between the two aromatic rings. 8, 10 6.373.05 12345678910111213141516 H 1 Figure 1-3 Chemical shift ( 1 H NMR) and charge transfer complex of [2.2]paracyclophane In [2.2] paracyclophane, the aromatic proton signal appears at 6.37 ppm, shifted about 0.5 ppm upfield from that of p-xylene. 9 This is due to a shielding effect from the ring current of the benzene ring on the opposite deck. According to Cram, 10 the stereochemical course of several polar addition and substitution reactions at the bridge position of [2,2] paracyclophane system is best

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4 explained on the basis of a species similar to 1. The cation positive charge can be distributed over both aromatic rings to compensate for the bond angle strain. Figure 1-4 shows the approximate structure based on the x-ray crystal structure. 11 The intermolecular separation (d) between the central carbon atoms of the two benzene rings is shortened to 3.09 (the normal Van der Waals separation between parallel benzene rings is set at 3.40 as a minimum). The two benzene rings are in boat configuration. This is attributed to a considerable transannular overlap. The bridge bond length is unusually large, 1.630 at 291 K (X-ray structure analysis was taken at 93 K) to compensate for the transannular steric and electronic repulsion. Figure 1-4 Geometry of [2, 2] paracyclophane 11 The bond angle and bond length deformations, as well as the face to face compression of two benzene rings, lead to high ring strain in cyclophanes. Boyd measured the heat of combustion of cyclophanes 2, 3, 4 (Figure 1-5), and determined their strain as 12, 31, 23 kcal/mol, respectively. 6, 12-14 234 Figure 1-5 Different bridge connection of [2.2]cyclophane

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5 Chemical vapor deposition (CVD) polymerization of [2.2]paracyclophane (Figure 1-6), 15 at 550 and 0.5mm pressure can form a thin, tough, polymer film called parylene on the objects with true confirmality of the coating to all surfaces including deep penetration into small spaces. This film has been found to be useful at temperatures up to 130 o C. 16 nheat, CVD2n H2C H2C * 2n H2C H2C Figure 1-6 Chemical vapor deposition (CVD) polymerization 1.1.2 Other Cyclophanes Nonbenzenoid aromatic compounds, such as azulene, tropolone, etc, are also important in aromatic chemistry. These compounds have interesting deformation structures caused by bridging. The charge transfer effects and electron cloud interactions can be examined by bringing two nonbenzenoid rings together. Cyclophanes which contain tropylium ions have been synthesized to test the charge-transfer interactions. 17, 18 When the tropylium rings are placed in a face-to-face position (9) (Figure 1-7), the tropylium protons move to higher fields in the NMR spectrum(1.22 ppm) than those unbridged tropylium ions (=9.28 ppm). This high-field shift is attributed to the diamagnetic ring current effect of the benzene ring and the enhanced electron density due to a charge-transfer effect. The singlet protons of a benzene ring in stair-like compounds 7and 8 are at much higher fields than those in compounds 5, 6 and

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6 9( 1.2 ppm). The benzene ring protons in 5 and 6 are nonequivalent because of their fixed geometry (NMR time scale). The ring-flip of 8 does not occur until 120 o C, whereas the equilibration in two conformers of 6 happens at a higher temperature. H H H H H 7.767.196.008.49 H H 7.695.98 H H H H 7.43 H H H 7.638.76 H H H H 5.514.767.717.31 8.93 H H H H 4.55 8.847.20 H Me H H H 8.067.706.945.7095678 Figure 1-7 Effect on aromatic protons [2]Azuleno[2]phanes 10 and 12 (Figure 1-8) are 10 systems. 19, 20 The C(9)-C(10) bond (azulene numbering) is elongated, and the azulene ring and benzene ring in compound 10 are distorted up to 9 o and 13.8 o respectively. The distance between the single proton and the benzene rings in the intermediates for 10, 11, and 12 are estimated to be 1.20, 1.50, and 1.75 respectively depending on the different barriers to ring inversion, which stem from the extent of steric crowding in the intermediate between the single proton and the neighboring benzene ring.

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7 101112 Figure 1-8 Distances of two aromatic protons to the other benzene deck The cylcophanes with naphthalene rings and anthracene rings are of special interest, because naphthalene and anthracene have a more extensive aromatic core. It would be interesting to study the nature and extent of deformation of the naphthalene ring and anthracene ring, the strain energy, and static and dynamic stereochemistry, as well as charge transfer effects between neighboring aromatic units. Naphthalenophane 13 was first synthesized in low yield from [2, 2] paracyclo-phane by the annulation method in 1963 (Figure 1-9). 9 Then, Wasserman and Keehn reported the synthesis by coupling the p-xylene in situ from the pyrolysis of quaternary ammonium salt with silver oxide in 41% yield, 21, 22 which is an antiand synmixture NMe3 NMe3 BrBr + Xylenereflux, 10h S S hv(EtO)3P 13 Figure 1-9 Synthesis of [2.2][1,4]naphthalenoparacyclophane

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8 that can be separated by crystallization. The optimum procedure to produce 13 would be using the photochemical sulfur extrusion method with triethyl phosphate as a solvent. 23 A considerable number of investigations have been made into the chemistry of [2.2](1,4) naphthalenophanes. The synand antiisomer 14 and 15 were first synthesized by elimination-cycloaddition of 4-methyltrimethylammonium hydroxide in 3% yield (Figure 1-10) each. 24 The anticonfiguration was confirmed by an alternate nine-step synthesis, in which only antiisomer was generated. Wasserman and Keehn modified the procedure and got 40% antiisomer and 4% synisomer. 21 A highly efficient route to compound 15 was designed by Brown and Sondheimer, 25 which involved the solvolysis of the corresponding ditosylate 16. 1415 CH2OTs CH2OTs 16 Figure 1-10 Synthesis of [2.2](1,4)naphthalenophane Anthracenophanes are virtually 1,4or 9,10-disubstituted anthracenes, which have lower ionization potential than naphthalene or benzene. Golden first reported [2.2] (9,10)-anthracenophane (17) (Figure 1-11) in 1961. 26 The synthesis and electronic absorption and emission spectra of five member ring incorporated anthracenophanes (18) were reported in 1977. 27, 28 X X=O, S 1718 Figure 1-11 [2.2]Anthracenophane and [2.2](2,5)heterophanes

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9 CO2Et CH3 CH2Br CH3 CH2NMe3 CH3 OH 1) LiAlH42) PBr31) NMe32) Ion exchangeresin 19 Figure 1-12 [2.2](1,4)Athracenophane In order to study the effect of transannular -electron interactions in excimer fluorescence, photodimerization, and ESR phenomena, Misumi et al. 29, 30 have synthesized many cyclophanes which incorporate anthracenes. The first compound in this series was synthesized from dimerization of 1,4-anthraquinodimethane, in turn derived by a Hofmann elimination of a quaternary ammonium hydroxide (Figure 1-12). The antiisomer (19) was obtained in 14% yield. Other cyclophanes, such as heteroand meta-cyclophanes were also synthesized. 31 Replacing benzene rings with pyridine rings results in [2.2](2,6)pyridinophane 20 (Figure 1-13). 32 One of the pyrenophanes, [2.2](1,3) pyrenophane 21, was reported by Misumi at al., 33 as well as a few mixed, asymmetrical pyrenophanes. Porphyrine 22, which is very important in biological transformations, also has cyclophane characteristics and is considered a special cyclophane serial. 29 Calixarenes 23 belong to the [1 n ]cyclphane

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10 group; their basket-like shape was adapted to host-guest or receptor-substrate chemistry. 31 N N 2021 NNHNHN OH HO HO OH R R R R 2223 Figure 1-13 Highly condensed phanes 1.2 The Physical and Chemical Properties of Cyclophanes Unusual structural features help chemists understand molecules and pursue their structural distortion limit. The works in this field provide useful information in developing, confirming, and refining the theoretical underpinnings of science. Cyclophane chemistry has provided insight into the ways in which molecules distribute strain, the effects of strain on molecular reactivity, transannular effects on chemical stability and spectroscopic properties, and as well as the criteria for aromatic stabilization. The X-ray analysis of [2.2](1,4)paracyclophane reveals that the two benzene moieties are separated by a distance of 299 pm, which is much smaller than the usual -system van der Waals contact distance of 340 pm between the two parallel aromatic rings in crystals. 34 As shown (Figure 1-4), the bridged carbons are only 278 pm apart, and the

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11 center carbons are 309 pm, which means that the two aromatic rings are bent out of plane by an angle of 12.6 o It is obvious that two clouds pressed hard against each other should lead to additional steric repulsion between the two rings. One would intuitively assume that this steric repulsion would be relieved by lowering the number of interacting -electrons. In contrast, the bending does not unambiguously increase or decrease the electron ionization energies. 35 The benzene system would be deformed and decrease its aromaticity due to lack of planarity, thus, ionization should be facilitated. On the other hand, bending a -system would localize its bond, i.e., forms a more polyenic type of structure which would increase the ionization energy. Model calculations using localized orbitals have shown that out of plane deformations of ethylene have a negligible influence on its -1 ionization energy, as long as they do not exceed certain limits, typically about 20 o for bending and/or twisting modes. 36, 37 The deformation results in decreasing ionization energy if it is not compensated by the necessary admixture of low-lying 2s atomic orbitals to accommodate the bulge, which would increase the ionization energy. The study of -electron energies in a series of cyclophanes by photoelectronic (PE) spectra indicates that ionization energies of -electrons are affected by the substituent group in the benzene deck. 35 The mean ionization energy for the two HOMOs of methyl substituted benzenes decreased by 0.5 eV. The cyclophanes had a smaller decrease in ionization energy. The ionization energy of superphane is not close to 6 eV as expected, but rather 7.5 eV. The monobromine substitution in the benzene ring has negligible influence on the PE spectra, while the amino group shifted the PE band towards the lower

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12 field. Bridge octafluoro paracyclophane (AF4) is an extreme example. The fluorine substitution induced the ionization energy shifts up field from 1.0 to 1.3 eV for the corresponding orbitals. The analysis of PE spectra leads to the recognition of a novel consequence of the fluoro-effect. Cyclophanes involving higher aromatic systems have a lower ionization potential, especially cyclophanes with incorporated anthracene. The synand anti-isomers of [2, 2](1,4)naphthalenophanes 21, 38, 39 (Figure 1-14) can be interconverted by light. Irradiation of syn-isomer 25 in degassed benzene leads primarily to the anti-isomer 24, while continued irradiation of the 24 solution gives other products. Irradiation with light above intermediate 2 + 22 + 24 + 4 hv 254 nm-190oC >190oC24252626a27282920oChv 350 nmhv-hv Figure 1-14 Photo reaction of [2.2]naphthalenopahane

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13 290 nm gives intermolecular rearrangement product 28, which rearomatizes to 24 at room temperature with a half life time of 76 s at 20 o C. 28 is a kinetic product, because extended irradiation for 10 days at room temperature leads to the thermodynamically more stable product, dibenzoquinene 29, in 25-50% yield. This compound is confirmed by x-ray, and presumably arises through two sequential [2 + 2] additions (26a first then 26). Normal naphthalene does not react with oxygen, but anti-[2.2]paracyclonaph-thalene reacts with singlet oxygen to form transannular peroxide. 22 This is due to the deformation of the naphthalene ring by the strain. hv 374 nm220oCor hv 254 nm240oC303132 Figure 1-15 Photo and thermal reversibility of [2.2](1,4)anthracenophane [2.2]Anthracenenophanes (Figure 1-15) are fascinating compounds. Both the antiand synisomers (31 and 32) are synthesized from the dimerization of 1,4-anthraquino-dimethane. 30, 40 The syn-isomer 32 can be rearranged thermally to the anti structure 31. When light is used, the isomer 32 undergoes a rapid photo induced cyclization reaction to form cage compound 30, which is both thermally and photochemically reversible.

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14 The transannular effect on the spectroscopy of cyclophanes has been utilized in the chemical luminescence polymer. -Conjugated polymers having cyclophane derivatives as the key unit have been synthesized by Chujo et al. 41 These polymers were soluble in common organic solvents, and self standing thin films exhibit strong blue photophoto-luminescence in solution and strong bluish-green photoluminescence in solid state. 1.3 1, 1, 2, 2, 9, 9, 10, 10-Octafluoro[2.2]paracyclophane (AF4) Fluorine has the largest electronegativity, while its Van der Waals radius is just 10% larger than that of hydrogen. The replacement of hydrogen by fluorine does not cause much steric problem, but changes the bond dipolemoment dramatically. The C-F bond, which is the strongest among the carbon-halogen bonds, is the shortest next to the C-H bond but it is much stronger in energy. Accordingly, various types of perfluorocarbons are both thermally and chemically stable compounds in sharp contrast to perchlorocarbons. The electron cloud in the C-F bond is slightly polarized towards the fluorine atom, thus electron repulsion between unshared electron pairs of fluorine atoms is substantial. The characteristic features correspond to the stability of perfluorocarbons against biological, chemical and physical stimuli. 42 Perfluorocarbons have some salient physical properties, such as low boiling point, insolubility in water and hydrocarbons, and low surface tension. Bridge fluorinated cyclophane (AF4), as mentioned above, has some unique properties including its thermal and chemical stability. The synthesis of AF4 was a challenge in organic chemistry for almost half of a century. The first chemical synthesis of AF4 was published by Cram et al. in 1951, 14 in which a highly diluted system was used, and the reaction could not be scaled up. There are abundant derivatives of [2.2] paracyclophane and other cyclophanes, but the derivatives of AF4 are scarce. One reason

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15 for this is because of the lack of a large scale synthetic method for AF4. AF4 was commercially unavailable until Dolbiers group solved this problem in 2000. 43-47 The interest in synthesizing AF4 is mainly driven by the industrial application of this compound as a monomer for chemical vapor deposition (CVD) (Figure 1-6) polymerization of AF4, known in industry as parylene-HT. The C-F bond is not readily oxidized, and compounds with multiple C-F bonds exhibit greatly improved oxidative and thermal stability. The parylene-HT polymer has a much lower dielectric constant (2.25) and a higher thermal stability (0.3% weight loss/h at 450) as well as a lower moisture absorption, 48 compared to the parent non fluorinated parylene polymer. Parylene-HT film is expected to be an excellent insulator in Information Technology (IT) industry. F F F F F F F F Figure 1-16 Octafluoro[2.2]paracyclophane (AF4 ) Table 1-1 Structural features of AF4 and [2.2]paracyclophane 11 AF4 [2,2] Paracyclcophane (deg) 11.8 12.6 (deg) 12.6 11.2 c () 2.80 2.78 d () 3.09 3.09 e () 1.380 1.394 f () 1.577 1.569 The structure of AF4 11 is very similar to that of [2.2] paracyclophane. 2 Some key structural data are listed in Table 1-1 (also see Figure 1-16).

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16 After successfully solving the problem of the synthesis of AF4, Dolbiers group published several electrophilic substitution reactions of AF4. Nitration and dinitration of AF4 (Figure 1-17) gave nitrated AF4 derivatives, which were reduced to aminocompounds. Other functionalities can be introduced into the AF4 molecule by the Sandmeyer reaction or coupling reaction, which opened the way to AF4 derivatives 22 and fluorinated cyclophanes. 49-52 F F F F F F F F F F F F F F F F NO2 98%Fuming HNO3 F F F F F F F F F F F F F F F F O2N NO2 pseudo-para:pseudo-meta:pseudo-ortho = 1:1:1NO2BF4Supholane80oC3334 Figure 1-17 Nitration and dinitration of AF4 Because fluorine is the strongest electron-withdrawing element, the bridge fully fluorinated compound 1,1,2,2,9,9,10,10-octafluoro [2.2](1,4)paracyclophane (AF4) has different physical and chemical properties than the non-fluorinated parent compound. The effect of the neighboring aromatic ring electron cloud towards the reactivity of the other ring is also an intriguing issue. For example, unsubstituted [2.2] paracyclophane has a single 1 H-NMR absorption for the aromatic proton at = 6.3 ppm, while this peak in AF4 is shifted to = 7.3 ppm. When unsubstituted paracyclophane is treated with bromine and iron, monoor di-brominated [2.2] paracyclophane is the product,

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17 depending on the mole ratio of bromine. 24 There is no product under the same or harsher conditions in case of bridge fluorinated AF4. 51 When [2.2]paracyclophane was treated with fuming nitric acid in glacial acetic acid, a mixture of dinitro[2.2]paracyclophane was produced immediately. 53 In contrast, the corresponding dinitro-AF4 can only be realized by using a very strong nitration reagent, nitronium tertafluoroborate, in polar solvent sulfolane and heated to 80 overnight. 50 Fluorine substitutes deactivate the electrophilic substitution reactions of AF4 dramatically. On the other hand, the same electron withdrawing effect would make the aromatic protons more acidic in AF4 than that in the non-fluorinated parent compound, and making it easier to deprotonate from the fluorinated AF4. 1.4 Aryne Chemistry The existence of aryne was first reported by Stoermer and Kahlert in the Chemical Institute of University of Rostock over one century ago. 3-Bromobenzofuran was treated with base in ethanol, and 2-ethoxybenzofuran was the product, 2,3-dehydrobenzo-furan 35 (Figure 1-18) was postulated as the reactive intermediate. 54 Wittig and coworkers proved the existence of ortho-benzyne later in 1942. 55 O 35 O Br Base, ethanol O OCH2CH3 Figure 1-18 Generation of benzofuran aryne It was a milestone in benzyne chemistry that Roberts et al. found solid evidence of benzyne 36 in 1953. 56 1-C 13 Labeled benzene chloride was treated with potassium amide,

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18 and a 1:1 ratio products 1and 2aniline were isolated (Figure 1-19). Since then, aryne chemistry has been extensively studied and used in organic synthesis. C Cl C C C NH2 NH2 KNH2-KCl, NH3 NH3+36 Figure 1-19 C 14 Labelling experiment The triple bond in the intermediate is significantly weaker than the unstrained triple bond. Intermediate 36 is better described as a strained alkyne rather than a biradical because of its large energy gap between the singlet and triplet states of the biradical (37.5.3 kcalmol -1 ). 57 The formation enthalphy of the strained alkyne was 106.6 3.0 kcalmol -1 by Wenthold and Squires. 57, 58 The corresponding bond length found experimentally was 124 ppm which is close to triple bond length 120.3 ppm and its IR stretching absorption was 1846cm -1 59 Therefore, benzyne has alkyne-like reactivity. For example, the Diels-Alder reaction, [2+2] reactions, etc. The methods of benzyne generation as summarized in Figure 1-20. X H X Y X X M N N N NH2 N N N N CO2N2+ CO2H NH2 36 Figure 1-20 Methods of benzyne generation Benzene halide compounds were treated with a strong base such as an amide, 60 to remove the ortho-proton and generate benzyne via an anion. Dihalogen substituted benzenes 61 were treated with lithium or magnesium to give the corresponding ortho

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19 metal halogen benzene, followed by E1b like elimination to form the desired benzyne. Decomposition of benzenediazonium-2-carboxylate 62 is considered the best method of benzyne generation and generally used in organic synthesis. Deprotonation of 1-amino-benzotriazole derivatives by oxydation followed by extrusion of nitrogen to generate benzyne. 63, 64 The fluoride ion displacement of the trimethylsilyl group by utilizing the large Si-F bond energy gives a convenient route to benzyne under mild conditions (Figure 1-21). 65 SiMe3 OTf O O Bu4NF61% Figure 1-21 Aryne with furan The use of aryne in organic synthesis was well reviewed by Pellissier. 66 The reaction of arynes with lithioacetonitriles derivatives was important in the synthesis of the basic skeleton of ergot and alkaloids. 67, 68 Aminoisoquinolines were synthesized through aryne with two equivalents of 2-pyrridinylacetonitrile. 69 Heteroarynes can be generated in a similar manner and used in the synthesis of heterocyclic compounds. 70 When transition metals are present, metal-aryne complexes can be formed. The synthetic applications of metal-aryne complexes are limited due to the lack of a general and mild method for aryne generation. Recently, Castedo and Yamamoto have reported some examples of successful generation of metal-aryne complexes under mild conditions. Palladium catalyzed co-cyclisation of aryne with alkyne produced the phenanthrene derivatives exclusively in 63% yield (Figure 1-22). 71 Pena et al. also described the synthesis of phenanthrenes and naphthalenes by co-cyclization of arynes with alkynes. 72, 73 In their later work, electron deficient alkynes, such as hexafluoro-2-butyne and

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20 dimethyl acetylenedicarboxylate (DMAD) gave phenanthrene derivatives in the presence of Pd(Ph 3 P) 4 while with Pd 2 (dba) 3 naphthalene derivatives were separated in high yield. Finally, the intermolecular cycloaddition of arynes with DMAD can be made highly chemoselective and be easily switched between the formation of phenanthrenes and naphthalenes by appropriate catalyst selection. In addition, by the appropriate choice of catalyst, the reaction can be selectively directed either towards the co-cyclisation of one aryne molecule with two molecules of alkyne or to the reaction of two molecules of aryne with one alkyne molecule. 74, 75 TMS OTf R1 R2 R1 R2 Pd(OAc)2P(o-tol)3, CsF+ Figure 1-22 Co-cyclisation of arynes with alkynes to phenanthrene derivatives TMS OTf R Pd (5%)+Cl CsFR R R=H: 70% (100:0)R=Me: 70% (70:30)R=ph: 71% (73:23)+ Figure 1-23 Palladium catalyzed reactions of allyl chlorides with benzyne Yamamoto successfully used aryne as a highly reactive carbopalladation partner with allyl chloride to give phenanthrene derivatives in high yields (Figure 1-23). 76 In the same way, benzyne also successfully co-cyclized with alkyne-alkene. Aryne reacted with bis--allyl palladium complexes in an amphiphilic fashion to produce 1,2-diallyl benzene in high yields. 77 The reaction of an aryne precursor with

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21 allytributylstannane and allyl chloride in acetonitrile in the presence of 2.5 mol% Pd 2 (dba) 3 at 40 produces the corresponding diallyl benzene in 76% yield (Figure 1-24). The reaction mechanism is the insertion of Pd(0) to allyl chloride to form the -allyl palladium complex 37, which is converted to bis--allyl palladium complexes 38 via the reaction with allyltributylstannane. The addition of two allyl groups of 38 to the benzyne triple bond leads to the final products. TMS OTf Pd2(dba)3 2.5%+Cl CH3CN, CsF SnBu3 + 76% -Pd--Pd--Pd-3738 Figure 1-24 Palladium catalyzed reaction between allytributylstannane, allyl chloride, and benzyne The first 4,5-dehydro[2.2]paracyclophane aryne (Figure 1-25), reported by Cram in 1969, was generated from 4-bromo[2.2]paracyclophane 39 and gave three products. 24 The total yield of cyclophane aryne intermediates is less than 30%. The dibromide derivatives (40 and 41) show the same reactivity as monobromide to produce intermediate 42. Bis-aryne cannot be generated from dibromide derivatives. Br Br Br Br Br Br 39404142

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22 Br (CH3)3COK(CH3)2SO OC(CH3)3 OH OH SCH3 4%14%10%++ Figure 1-25 Paracyclophane aryne Bis-dehydro[2.2]paracyclophane 7 was generated from 4,5,15,16-tetrabromo[2.2]-paracyclophane (Figure 1-26) by Cram. Br Br Br Br O O n-BuLi, Et2O-78 oCO 84% Figure 1-26 [2.2]Paracyclophane bis-aryne The perfluorinated o-benzyne had been isolated in cryogenic matrices by photolysis of the corresponding phthalic anhydride, 78, 79 and the CASSCF calculation showed that the singlet-triplet energy gap of tetrafluoro-o-benzyne was larger than that of non-fluorinated benzyne by several kilocalories per mole. 79 Radziszewski et al. 80 identified the CC bond stetching vibration of tetrafluoro-o-benzyne at 1878cm -1 while the length of that is similar to CC bond. The chemistry of fluorinated benzyne differs significantly from that of none fluorinated one, the former is much more electrophilic and reactive. For example, tetrafluoro-o-benzyne reacted readily with thiophene. 81, 82

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23 Other benzynes, such as meta-, para-benzynes and heteroarynes, were also studied extensively and summarized in an excellent review article by Wenk et al. 83 Benzyne chemistry has been studied for over one century and is still a very active research field. Exploring different aryne generation methods will bring new features into aryne chemistry and help us understand more about its chemical reactivity. Bridge fluorinated paracyclophane has just become commercially available recently, and studying the AF4 derivatives would be cheaper than it was before. AF4 derivatives will also bring new feature into cyclophane chemistry and reveal more electronic effects in cyclophane chemistry. These derivatives may also service as new synthon for other fluorinated cyclophanes.

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CHAPTER 2 4,5-DEHYDROAND 4,5,15,16-BIS-DEHYDROOCTAFLUORO[2.2]PARACYCLOPHANES: FACILE GENERATION AND EXTRAORDINARY DIELS-ALDER REACTIVITY 2.1 Introduction Benzyne was first discovered over a century ago by Stoermer and Kahlert, 54 while the landmark in benzyne chemistry is the isotopic labeling studies on the KNH 2 mediated reaction of chlorobenzene, which left little doubt on the existence of benzyne as a highly reactive intermediate. 56 The most striking feature of these dehydroaromatic intermediates is their dienophilic reactivity with other aromatic systems as diene partners. Depending on mode of generation and the nature of the aryne component, however, the yields in these Diels-Alder type reactions can often be modest or poor. 60 For example, 75% is the best yield reported for benzyne addition to anthracene, considered one of the most reactive aromatic substrates in Diels-Alder reactions with arynes. 84, 85 In that case, the benzyne was generated from benzenediazonium carboxylate, which is generally considered to be among the best methods for carrying out Diels-Alder chemistry involving benzyne. 86 Benzene is a much poorer Diels-Alder substrate, and it yielded only 9% Diels-Alder adduct in a similar reaction with benzyne, 87, 88 although its reactions with tetrafluorobenzyne and tetrachlorobenzyne (among the more reactive arynes) yielded 33 and 62% of adduct, respectively. 89, 90 Examples of 4,5-dehydro-[2.2]paracyclophanes in the literature are rare. The parent 4,5-Dehydro[2.2]paracyclophane appears to have been mentioned but once, in 1969 when Longone and Chipman reported its generation by potassium t-butoxide promoted 24

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25 dehydrobromination of 4-bromo-[2.2]paracyclophane in t-butylbenzene in the presence of excess anthracene, with only a 15% yield of Diels Alder adduct being obtained. 24, 91 Their yield is similar to that obtained in Cadogans original report of the use of this method to generate benzyne from bromoaromatics, in which he obtained high yields of t-butyl aryl ethers, but, when generated in the presence of anthracene only produced 21% yield of tripticene. 92 Although the Longone and Cram papers are the only mentions of dehydro[2.2] paracyclophanes in the literature, there also exists another report by Cram in 1969 of a bis-dehydro[2.2]paracyclophane, 7 where sequential aryne-furan Diels-Alder reactions of the nominal 4,5,15,16-bis-dehydro[2.2]-paracyclophane was carried out via the double dehalogenation of 4,5,15,16-tetrabromo[2.2]paracyclophane (Figure 2-1). BrBrBrBrn-BuLi, Et2O-78 oCOOO84% Figure 2-1 Bis-paracyclophane aryne with furan reaction Because of competitive trapping by the nucleophilic t-butoxide, the use of Cadogans t-butoxide method to generate arynes has almost never been used to initiate Diels-Alder chemistry. Following the successfully solving the AF4 synthetic issue, we applied these conditions for dehydroiodination 4-iodo-1,1,2,2,9,9,10,10-octafluoro[2.2] paracyclophane 2 to mono-AF4-yne 1, 49, 52 and the sequential double dehydroiodination of 4,15-diiodo-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane 18 to bis-AF4-yne 17 50 (Figure 2-2) which led to efficient Diels-Alder trapping of the intermediate arynes with virtually no observed competitive interception of the intermediates by the t-butoxide ion.

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26 F F F F F F F F 1 F F F F F F F F 17 Figure 2-2 Monoand bis-AF4-yne 2.2 Results and Discussions 2.2.1 Synthesis of Aryne Precursors The 4-iodoand 4,15-diiodooctafluoro[2.2]paracyclophane precursors were prepared from 1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane (AF4) by improved procedures based on those previously published (Figure 2-3). 51, 52 Noteworthy is the double-nitration procedure, in which essentially equal amounts of the pseudo-ortho (4,12-dinitro-), pseudo-meta (4,15-dinitro-), and pseudo-para (4,16-dinitrooctafluoro[2.2] paracyclophane) products (23a, b, and c, respectively) are formed. The pseudo-meta and pseudo-para isomers are readily separated from the pseudo-ortho isomer by column chromatography, and it is this mixture of 4,15and 4,16-dinitro isomers (23a and 23b, respectively) that is used in subsequent steps to eventually synthesize a mixture of 4,15and 4,16-diiodooctafluoro-[2.2]paracyclophanes (18a and 18b, respectively). Since both of these isomers lead to the same bis-aryne (17), this mixture was used as the "precursor" of 4,5,15,16-bis-dehydrooctafluoro[2.2]paracyclophane. The reduction of nitro compound by palladium (10%) on carbon with hydrogen at room temperature gives quantitatively yield. Product was filtered through a short pad of silicon Gel to get rid of palladium and carbon, while no further purification is necessary. Chromatography purification was required for other reduction methods and the yield was much lower.

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27 F F F F F F F F F F F F F F F F F F F F F F F F NO2 F F F F F F F F NH2 90% HNO3I Pd/C, Methanol, H2a) 0oC, NaNO2, H2SO4 HOAcb), KI/H2O, RT, 8h 2 F F F F F F F F F F F F F F F F X X 5 equiv, sulfolane 80oC25, X=NO225a, pseudo meta25b, pseudo para25c, pseudo ortho, 23% 49%25a&b26a&b (X=NH2)26a&bpseudo meta, 18apseudo para, 18b (X=I)68% Pd/C, Methanola) 0oC, NaNO2, H2SO4 HOAc, H2Ob) KI/H2O, RT, 8hNO2+BF4-H2 Figure 2-3 Synthesis of precursor 2.2.2 Reactions of 4, 5-Dehydrooctafluoro[2.2]paracyclophane, 1 When monoiodide 2 was treated with potassium t-butoxide in refluxing benzene, in refluxing t-butylbenzene in the presence of stoichiometric amounts of naphthalene or anthracene, the corresponding Diels-Alder adducts were obtained (Table 2-1), yields are from 60% to 88% (Figure 2-4). The yields obtained with benzene and naphthalene are the largest yet reported for aryne reactions with these substrates. The structural integrity of compounds 3-5, as well as the stereochemistry of compound 4, were demonstrated by NMR as illustrated below for the representative adduct 5. In the proton spectrum of 5, the signals at 6.96, 7.32 and 7.27 ppm are the

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28 second order multiplets that are characteristic for an ortho-phenylene group. The proton at 7.65 has an extra coupling, most likely a through-space coupling with fluorine. Of the three remaining aromatic CHs the two with protons at 7.20 and 5.84 are on the same aromatic ring as revealed by their mutual 1 H13 C long-range couplings. The final aromatic proton, at 6.72, displays a nOe with the proton at 7.20, leaving the signal at 5.84 to be assigned as those facing the moiety originating from anthracene, and indeed the signal at 5.84 displays nOes with the protons at 7.27 and 7.65, and no nOes with those at 7.32 and 6.96. In a similar fashion, in compound 4, the proton at 5.78 ppm, displays nOes with those at 7.27 and 7.59, and no nOe with the alkene proton at 6.93, proof for the endo stereochemistry. The upfield chemical shift of 5.78, which is comparable with the 5.84 signal in compound 5 and significantly smaller than the 7.16 signal of the parent cyclophane, is diagnostic for its position above the plane of an aromatic ring. The chemical shift of the corresponding proton in compound 3, 6.91 ppm, demonstrates that significantly less shielding is to be expected for a proton having a similar position above a double bond. Interestingly, no products deriving from nucleophilic capture of the presumed aryne intermediates by the excess t-butoxide base were detected in any of these reactions, even when the reaction was carried out in refluxing t-butylbenzene with no substrate added. In this case a surprisingly high (78%) yield of the DA adduct (6) with t-butylbenzene was obtained. This is in contrast to Longone and Chipmans results, 91 as well as those of Cram and co-workers, 24 where t-butoxide adducts were found to be a major side product in each of their respective studies where this method of aryne generation was used.

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29 FFFFFFFFI FFFFFFFF FFFFFFFF FFFFFFFF 2345128.8134.1118.8119.9127.3146.845.7137.6141.8126.37.267.056.916.786.605.48129.07.597.275.756.936.707.225.78128.8127.6134.0118.7119.8128.5145.247.6141.1143.3125.3125.8127.3128.9127.9134.0118.7120.1128.2128.7144.450.3144.4142.7124.5126.1125.7126.57.657.27 6.01 7.326.966.725.847.2022(86%)(86%)(84%) naphthalene t-BuOKt-butylbenzene, reflux benzenet-BuOK, reflux anthracene t-BuOKt-butylbenzene, refluxFFFFFFFF 6128.9128.6133.9128.9129.0120.0120.0126.3147.346.8137.4138.3130.3130.3134.3126.934.727.6147.5126.645.57.287.246.976.907.067.026.196.625.435.390.936.62 2 t-BuOKt-butylbenzene, reflux(78%) Figure 2-4 Diels-Alder reaction of AF4-yne

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30 Table 2-1. Diels-Alder reactions from treatment of 4-iodooctafluoro[2.2]paracyclophane, 1, with potassium t-butoxide. Substrate Solvent T() Time (min) Product ( %) benzene benzene reflux (80) 20 3 (86) naphthalene butyl ether reflux (142) 20 4 (88) anthracene t-butylbenzene reflux (169) 15 5 (84) t-butylbenzene t-butylbenzene reflux (169) 40 6 (78) 1,4-dimethylnaphthalene butyl ether reflux (142) 30 7(60) (4.55:1/endo:exo) 2,3-dimethylnaphthalene butyl ether reflux (142) 30 8(67) 2-methoxylnaphthalene butyl ether reflux (142) 30 9:10:11(18:4:27) furan t-butylbenzene reflux (142) 20 12a & b (80) 2,5-diphenylfuran butyl ether Reflux (142) 30 13(84) [2.2]paracyclophane t-butylbenzene reflux (169) 20 14 (86) bicyclo[2.2.1]hepta-2,5-diene butyl ether reflux (142) 30 15 & 16 (67) The stereoselectivity exhibited by 1 in its virtually exclusive formation of the endo-isomer (4) from naphthalene addition is remarkable, particularly since both molecular mechanics and AM1 calculations predict only a very slight thermodynamic preference for this isomer (0.75 and 0.02 kcal/mol, respectively). 49 The endo transition state may be favored because of a stabilizing herringbone Hinteraction 93 of the 5.78 ppm protons that interact with the cloud of the endo benzene ring. This hypothesis were further supported by AF4-yne reactions with 1,4-Dimethylnaphthalene and 2,3-dimethyl-naphthalene. In 1,4-Dimethylnaphthalene reaction (Figure 2-5), product 7a&b were

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31 obtained in 60% yield, in which aryne added exclusively to the ring without methyl substitutes due to the steric effects. It is interesting that the product ratio of endoand exois about 100:37 with the more bulky aromatic ring inside. When 2,3-dimethyl-naphthalene was the substrate, as expected, adduct 8 was produced in 67% yield, which has a better electronic match with the electron deficient dieneophile, AF4-yne. FFFFFFFF 6.51127.5128.5120.4145,47.07128.6119.1134.45.65127.918.12.49141.46.86127.4131.36.79141.543.95.92 FFFFFFFF 7.13129.0134.2119.0145.76.55127.4120.16.91129.4 44.25.87137.57.066.54126.5143.518.12.23137.6130.17a7b FFFFFFFF 7.12128.97.47124.7 6.61127.1127.9120.0144.916.51.645.2253.5143.1133.97.18125.7141.2118.75.65127.6 8 Figure 2-5 Products of 1,4-dimethylnaphthalene and 2,3-dimethylnaphthalene The reaction of AF4-yne with 2-methoxynaphthalene gave three products 9, 10, and 11(Figure 2-6) which comply with the electronic requirement: the addition occurred mostly on the electron rich aromatic ring (totally 45% yields). The enol ether 9 was

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32 hydrolyzed to give ketone product 11(27%). Only 4% adducts 10 occurred on the other aromatic ring. F2C CF2 CF2 CF2 CF2 F2C 11910OCH3 F2C CF2 CF2 F2C O F2C CF2 O Figure 2-6 Products of 2-methoxylnaphthalene with AF4-yne Furan has generally been considered to be a good Diels-Alder diene substrate in trapping reactions with arynes. Indeed, when iodide 2 was treated with potassium t-butoxide in refluxing t-butylbenzene in the presence of 1.1 equivalents of furan, an almost 50:50 mixture of the endoand exo-adducts 12 a&b of furan to aryne 1 was obtained in 80% yield. The two isomers were distinguished by NMR (vide infra), but a corroborative X-ray crystal structure of the endo-adduct was also obtained. Interestingly, in case of 2,5-diphenylfuran reaction with AF4-yne, the exoand endoratio of two products 13a:13b is 76:24 with exo-product predominant (Figure 2-7).

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33 FFFFFFFF 12a134.2119.3127.7147.5140.6127.981.45.887.41128.87.296.51118.7FFFFFFFF 12b129.2118.9134.8129.7119.4150.4144.1127.381.07.227.336.996.65127.15.91O 128.56.76O FFFFFFFF O FFFFFFFF O 13a13b7.20128.3135.0130.27.336.64127.2118.6119.1127.7152.694.7135.0148.37.25127.27.85128.37.56na7.50 Figure 2-7 Products of furan and 2,5-diphenylfuran with AF4-yne There have been few previous reports in the literature of aryne additions to a [2.2] paracyclophane. Perhaps the best example is Heaneys study of tetrafluorobenzyne, where he got a yield of 44% of its addition to [2.2]paracyclophane in 1969. 94 Such a reaction also posed no problem for aryne 1, which, under the usual conditions, underwent Diels-Alder addition to the hydrocarbon [2.2]paracyclophane in 84% yield (Figure 2-8). Although fully characterized by NMR (vide infra), an X-ray crystal structure of adduct 14 was also obtained. The regiochemistry of addition observed in the formation of adduct 14 was consistent with that reported earlier for the tetrafluorobenzyne/[2.2]paracyclophane adduct.

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34 FFFFFFFF 14 Figure 2-8 Product of [2.2]paracyclophane with AF4-yne (bold shifts on this structure indicate protons pointed toward the viewer) Bicyclo[2.2.1]hepta-2,5-diene (norbornadiene) may act as diene or dienophile depending on the reaction conditions and substrates. Stereochemistry of norbornadiene in the DA reaction has been extensively studied, 95-97 and there have been a few studies of benzyne additions to norbornadiene. Both [2+2] and [2+2+2] addition products were obtained for the reactions of tetrafluoroand tetrachloro-benzyne with norbornadiene, with ratios of 6:1 and 3:1, being observed respectively. 98 The ratio of [2+2] and [2+2+2] products did not change with the pressure of the reaction of tetrachlorobenzyne, which was generated from butyllithium with hexachlorobenzene, with norbornadiene. 99 The reaction of AF4-yne with bicyclo[2.2.1]hepta-2,5-diene was examined to determine its preferred selectivity. Four products (Figure 2-9), exoand endo-[2+2+2]addition products 15 a&b, endoand exo-[2+2]addition products 16 a&b were obtained in a total yield of 67.6% in butyl ether. The ratios of products 15a:15b:16a:16b is 62:27:3:8, with [2+2+2] products being predominant. When reaction was carried out in neat norbornadiene, the ratios of products changed to 74:12:10:4. This observed preference for [2+2+2] products contrast with the regioselectivity of other arynes with norbornadiene. In

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35 addition, all the major products are formed from the endo-addition to norbornadiene. The endo selectivity for both types of products should be noted. FFFFFFFF 7.27130.0FFFFFFFF 7.14128.3 FFFFFFFF FFFFFFFF 15a15b16a16b Figure 2-9 Products of bicyclo[2.2.1]hepta-2,5-diene with AF4-yne No adducts were able to be observed with other alkenes under these conditions, neither [2+2] or Ene reaction being seen. Reactions with 1-octene, cyclohexene, t-butylethylene and 1,3,5-cycloheptatriene were all attempted with neither [2+2] or ene reaction being observed. instead, the AF4-I was observed to convert largely to AF4. Mechanistic ramification of this adduct will be discussed further in next chapter. 2.2.3 Reactions of 4,5,15,16-Bis-(Dehydro)octafluoro[2.2]paracyclophane, 17 Incredibly, the yields of bis-adducts obtained from the sequential bis-dehydro-iodination of diiodide 18a and 18b under analogous conditions were comparable to those

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36 for the mono-adducts! Adducts 19-22 (Figure 2-10) were thus obtained in 83, 86, 80 and 84 % yields, respectively. Reaction conditions and results were listed in Table 2-2. All adducts were fully characterized by 1 H, 19 F, and 13 C NMR, and an X-ray crystal structure was obtained for bis-naphthalene adduct, 20. Again, the highly shielded aromatic protons of the AF4 benzene ring that face the endo benzene rings of adducts 20 and 21(=5.24 and 5.38 ppm, respectively) are noted with interest. Table 2-2. Diels-Alder reactions from treatment of 4, 15-diodo-octafluoro [2.2]paracyclophane, 18, with potassium t-butoxide, in refluxing solvent. Substrate Solvent Temperature ( o C) Time (minutes) Product (%) benzene benzene reflux (80) 150 19 (83) naphthalene butyl ether reflux (142) 30 20 (86) anthracene t-butylbenzene reflux (169) 30 21 (80) [2.2]paracyclophane t-butylbenzene reflux (169) 30 22 (84) 2.2.4 NMR Discussion. 100 The structural integrity of most compounds and the stereochemistry of compounds 4, 6, and 12 a&b were demonstrated by NMR. The numerous nOes on such rigid structures were diagnostic for stereochemical assignment. Of the three pairs of vicinal protons originating from compound 2 (e.g., 6.47 and 6.47, 7.18 and 7.22, and 6.73 and 6.78 ppm for adduct 14), the one on the formerly benzyne ring (6.47 and 6.47 ppm) can be identified by its couplings to the carbons at ca. 147 ppm, carbons that in turn couple to protons originating from the arene (4.54, 4.48, 5.63, and 5.94 ppm) NOes with this pair (6.47 and 6.47 ppm) identified the pair (7.18 and 7.22 ppm) syn to it. Long-range couplings between the protons and the carbons in the para-phenylene ring of 14 allowed

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37 the assignment of the pair anti to the protons originating in the benzyne ring of 1 (6.73 and 6.78 ppm, meta to 7.22 and 7.18 ppm, correspondingly). FFFFFFFFI FFFFFFFF benzenet-BuOK, refluxFFFFFFFF FFFFFFFF FFFFFFFF FFFFFFFF 22a22b1920212.772.493.083.056.922.562.962.392.204.444.496.935.616.046.015.965.987.19125.3126.47.59143.15.9650.4144.4124.47.30126.06.94119.9128.1144.65.38124.47.20125.6124.97.535.6947.4140.96.89145.3127.5120.05.24124.3143.87.05138.05.4845.6141.56.78120.2126.8146.86.29124.6I m, or p-diiodo AF4 Figure 2-10 The bis-Diels-Alder reaction of AF4-yne In compound 14, 6.78 displayed a nOe with 5.94 and 4.48 ppm, which in turn displayed nOes with 7.07 and 6.96 ppm. Other NOEs afforded positive stereochemical assignment of the aliphatic protons, e.g., 2.88 ppm displayed nOes with 5.94, 6.78, and 7.07 ppm. Compounds 22 a&b were analyzed as a mixture. The fragments originating from [2.2]paracyclophane displayed very similar proton chemical shifts in both 14a and 14b.

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38 The protons originating from the fluorinated aryne 1 display two ABs of roughly the same intensity (6.04, 5.96 and 6.01, 5.98 ppm) indicative that 22a and 22b are formed in equal amounts. Low solubility precluded obtaining ghmbc spectra. The structural integrity of these compounds was confirmed by nOes similar to those observed for compound 14. For the furan adducts 12 a&b, the major isomer was assigned as 12a on the basis of the nOes between the protons at 6.76 ppm (identified as anti to the protons originating from the aryne ring of 1 as mentioned above) and the protons at 7.29 ppm, originating in the furan. Isomer 6 would be expected on steric grounds, and the exo-structure was unambiguously confirmed on the basis of nOes that were observed between the cyclophane protons that are pointed toward the former tert-butylbenzene (6.97 and 6.90 ppm) and the vinylic protons at 7.02 and 7.06 ppm. In a similar fashion, in compound 4, the proton at 5.78 ppm displays nOes with those at 7.27 and 7.59 ppm and no nOe with the alkene proton at 6.93 ppm, proof for the endo stereochemistry. 2.2.5 X-ray Discussion. Some of adducts were analyzed by X-ray diffraction (Appendix). Crystal structures of anthracene adduct and bis-naphthalene adduct were demonstrated below. The crystal structure of the anthracene adduct 5 (Figure 2-11 and also Appendix Figure 2) indicates that, although there are several ways for the AF4 moiety to be distorted upon derivation, the main impact is that the torsion angles around the bridging C7-C8 and C15-C16 moieties (for example, the C6-C7-C8-C9 torsion angle, as seen in Figure 2-11) open to

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39 values of 26.5 and 27.0 respectively. This is accomplished by twisting the phenyl rings by an angle of 11.6 around an axis perpendicular to them. Figure 2-11 ORTEP drawing of anthracene adduct 5 and endo furan adduct 12a According to the X-ray structure of endo furan adduct, 12a (Figure 2-11 and also Appendix Figure 3), the distortion parameters of its AF4 moiety involve bridging torsion angles of 12.6 and 21.9 with a twist angle of 7.7 whereas for [2.2]paracyclophane adduct 14 (Figure 2-12 and also Appendix Figure 1), the bridging torsion angles are 14.1 and 22.1 two phenyl rings of AF4 moiety have a twist angle of 14.9 o connected to [2.2]paracyclophane and 8.1 o on the other one. Figure 2-12 ORTEP drawing of [2.2]paracyclophane adduct 14 and bis naphthalene adduct 20

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40 The X-ray analysis of bis-naphthalene adduct 20 (Figure 2-12 and also Appendix Figure 4) indicates that there are two molecules of 20 in its asymmetric unit. For molecule A, the bridging torsion angles are 28.0 and 30.1 with a twist angle of 12.4 whereas for molecule B the bridging torsion angles are 27.7 and 28.9 with its twist angle being 23.1 In summary, there is a trend observed in these X-ray structures when considering how the AF4 moiety is distorted in order to relieve the strain of adding a large substituent to the benzene rings. Small variations in the dihedral angles between the benzene rings of each of the four crystal structures of from 1.2 to 4.9 are observed. More significantly, and presumably in order to minimize nonbonded interactions, the benzene rings twist around an axis perpendicular to the benzene rings, with more twist being observed for larger substituents. Such twist is coupled with an opening of the bridging torsion angles of the CF 2 -CF 2 units. 2.3 Conclusion On the basis of the results that have been presented, it can be concluded that the reactive arynes, 1 and 17, have been generated and are responsible for the chemistry observed and discussed. The relative ease of their generation (refluxing benzene) can be ascribed to an increase in acidity of the proton vicinal to the halogen, induced by the highly electronegative fluorinated bridges. The fluorinated bridges of 1 and 17 should also make them highly electrophilic and therefore more reactive arynes (compared to the nonfluorinated dehydro[2.2]paracyclophane). However, such high electrophilicity should also lead to enhanced reactivity with nucleophiles such as t-butoxide ion, which is not observed. At this time, the only potential explanation we have for the chemoselectivity

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41 exhibited by arynes 1 and 17 is the possible electrostatic repulsion of the t-butoxide nucleophile by the fluorinated bridges of the two arynes. The base used in aryne reactions above is not soluble in above system, which means that reactions occur heterogeneously. Heterogeneous characteristics may also explain the absence of t-butoxide ion addition product, which is a major product in Cadogans early report. Other aspect of the reaction mechanism will be discussed further in the next chapter. 2.4 Experimental General Methods. 1 H (500 MHz), 13 C (126 MHz), and 19 F (282 MHz) NMR spectra were recorded using CDCl 3 as the solvent, and chemical shifts ( values) were measured relative to the signals for CHCl 3 CDCl 3 and CFCl 3 respectively. 1 H and 13 C chemical shift data are directly indicated on the structures of the adducts in the Results and Discussion section above, whereas 19 F NMR data are provided in the Experimental Section below. X-ray crystal analyses were performed by the Center for X-ray Crystallography and HRMS and CH micro elemental analyses by the Spectroscopic Services Group at the University of Florida. Column chromatography was performed using chromatographic silica gel, 200-425 mesh, as purchased from Fisher, unless otherwise mentioned. 4-Nitro-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane. Into 200 mL of 90% nitric acid was added 10.0 g (2.8 mmol) of AF4 in one batch. The mixture was stirred overnight, after which it became a clear solution. This solution was then added to 500 g of ice in an Erlenmeyer flask, and a white precipitate formed. The mixture was filtered to give 10.0 g (90%) of the yellow-white mononitro product, 23. 52

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42 Isomeric Dinitro-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophanes. Explicitly following the published procedure, 51 22.1 g (166 mmol) of nitronium tetrafluoroborate undergoes reaction with 10.2 g (29 mmol) of AF4 in sulfolane (100 mL) in an overnight reaction at 80 to form a white solid product when poured into ice. Column chromatography (hexane/ethyl acetate, 10:1) gave 6.3 g (49%) of an almost 1:1 mixture of the 4,15and 4,16-dinitrooctafluoro[2.2]paracyclophanes, 25a and 25b, respectively, along with 3.0 g (23%) of the 4,12-dinitro isomer. 4-Amino-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane, 24. A anhydrous methanol (100ml) solution of 23 (3.0 g, 7.6 mmol) was added ammonium formate (7.2g, 114mmol) and Pd/C (0.24g, 0.23mmol) under nitrogen at room temperature. 101 The mixture was purged with hydrogen three times, and then a hydrogen balloon was attached to it. After stirring the reaction mixture overnight, solution was filtered over a short pad of silica Gel. The solvent was evaporated to give 2.55 g amine 24 in yield of 91%. Mixture of 4,15and 4,16-Diamino-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclo-phanes, 26a and 26b. Likewise, 0.51 g (1.15 mmol) of the mixture of 25a,b was converted to 0.39 g (89%) of a mixture of pseudo-meta and pseudo-para diamines, 26a and 26b, respectively. 4-Iodo-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane, 2. 52 A solution of amine 16 (1.9 g, 5.2 mmol) in acetic acid (4 mL) was cooled to 0 in an ice/brine bath. Ice (1.5 g) and 1.5 mL of H 2 SO 4 were added with stirring, and ensuring that the temperature was still below 0, Na NO 2 (2.0 g, 29 mmol) was added in one batch. After the reaction was stirred for 2 h at 0, it was poured, with vigorous stirring, into 10 mL of an aqueous

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43 solution of KI (5.2 g, 30.8 mmol) at room temperature. After stirring overnight, the mixture was filtered and the solid purified by column chromatography (alumina, hexane/EtOAc, 50:1) to give 1.7 g (67%) of the 4-iodo product, 2. Mixture of 4,15and 4,16-Diiodo-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclo-phanes, 18a and 18b. 51 A solution of the mixture of 4,15and 4,16-diaminooctafluoro [2.2]paracyclophanes, 26a and 26b, respectively, (2.0 g, 5.2 mmol) in acetic acid (4 mL) was cooled to 0 in an ice/brine bath; ice (1.5 mL) and concentrated sulfuric acid (1.5 mL) were added with stirring. With the temperature maintained below 0, sodium nitrite (2.0 g, 29.0 mmol) was added as quickly as possible to the solution. The reaction was stirred at this temperature for 2 h, and then the mixture was added to an aqueous solution (10 mL) of potassium iodide (5.2 g, 30.8 mmol) at room temperature with vigorous stirring. This mixture was kept stirring at room temperature overnight and then filtered with the solid being purified by column chromatography (hexane/ethyl acetate, 50:1) to give 2.2 g (68%) of a mixture of 18a and 18b. Generation of 4,5-Dehydrooctafluoro[2.2]paracyclophane, 1, and its Reaction with [2.2]Paracyclophane. Into a three-necked round-bottomed 50 mL flask were added iodide 2 (0.478 g, 1 mmol) and potassium t-butoxide (0.56 g, 5 mmol) along with 10 mL of dry t-butylbenzene under a nitrogen flow. Then, [2.2]paracyclophane (0.22 g, 1.1 mmol) was added and the mixture heated to 170 and refluxed for 20 min. The oil bath was then removed and the reaction product mixture examined by 19 F NMR. The reaction was worked up by filtering the mixture through a short pad of silica Gel, washed with 3X10 ml dichloromethane. Solvent was evaporated away, and products were further

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44 purified through silicon Gel column to give 86% yield of 8: mp 140-142; 1 H NMR (500MHz) (CDCl 3 /TMS): 7.22(d, J=8.7Hz, 2H), 7.18(d, J=8.4Hz, 1H), 7.07, 6.96(ABX, J=8.2, and 1.5Hz, 2H), 6.95, 6.93(ABX, J=8.1, 1.5Hz, 2H), 6.78, 6.73(AB, J=8.6Hz, 2H), 6.47(s, 2H), 5.94(d, J=6.2Hz, 1H), 5.63(d, J=6.6Hz, 1H), 4.54(ABX, J=6.3, 2.8Hz, 1H), 4.48(ABX, J=6.2, 1.8Hz, 1H), 3.12(ABX, J=12, 7.1, 2.6Hz, 1H), 2.98(ABX, J=13.2, 8.0, 4.0Hz, 1H), 2.88(m, 1H), 2.82 (DT, J=13.1, 7.9Hz, 1H), 2.58, 2.55(AB, J=7.9Hz, 2H), 2.38(ABM, J=15.1, 8.1, 4.1, 2.0Hz, 1H), 2.20(ABX, J=15.2, 8.1, 0.6Hz, 1H); 19 F NMR(282MHz, CDCl 3 /CFCl 3 ), four equal intensity AB quartets at -111.4 (J = 244.2 Hz) and -111.7 (J = 243.9 Hz), -115.0 (J = 243.9 Hz) and -115.7 (J = 244.2 Hz), -116.7 (J = 239.7 Hz) and -117.7 (J = 241.1 Hz), -119.4 (J = 240.8 Hz) and -119.9 (J = 239.7 Hz); HRMS calcd for C 32 H 22 F 8 558.1594, found 558.1594. Reaction of Aryne 1 with Anthracene. The procedure is the same as above, except that 0.18 g (1.1 mmol) of anthracene was used and the reaction was refluxed for 15 min. Two isomers, in a ratio of 93:7 (from 19 F NMR) were obtained in a total yield of 84%. The major isomer was isolated via silica gel chromatography (hexane/EtOAc, 100:1). Major isomer (5): mp 296-298; 1 H NMR (300MHz, CDCl 3 /TMS) Isomer 1 7.65(m, 2H), 7.32(m, 2H), 7.27(m, 2H), 7.20(s, 2H), 6.96(m, 2H), 6.72(s, 2H), 6.01(s, 2H), 5.84(s, 2H); 13 C NMR(126MHz, CDCl 3 ) 144.4, 142.7, 134.0, 128.9, 128.7, 128.2, 127.9, 126.1, 125.7, 124.5, 120.0, 118.7, 50.3; MS(EI): 528(M+, 76), 352, 301, 176, 69; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ), two equal intensity AB quartets at -111.4 (d, J = 243.9 Hz) and -115.1 (d, J = 243.9 Hz), -116.53 (J = 240.8 Hz) and -119.4 (d, J = 240.8 Hz); Anal. Calcd for C 30 H 16 F 8 : C, 68.18, H, 3.05. Found: C, 67.73; H, 2.86. Minor isomer: Isomer 2 7.76(s, 2H), 7.78(m, 2H), 7.52(m, 2H), 7.30(m, 2H), 7.18(s, 2H), 6.94(m, 2H), 5.80(m,

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45 2H), 5.64(s); 19 F NMR(282MHz, CDCl 3 /CFCl 3 ), two equal intensity AB quartets at -111.1 (d, J = 243.9 Hz) and -115.4 (d, J = 243.9 Hz), -116.3 (d, J = 237.7 Hz) and -119.5 (d, J = 240.8 Hz). Reaction of Aryne 1 with Benzene. The procedure is the same as above, except that the reaction was carried out in refluxing benzene at 80 for 150 min. The product was purified by silica gel chromatography (hexane/EtOAc, 100:1) with a 86% yield of 3: mp 144-146; 1 H NMR (500MHz, CDCl 3 ) 7.26(s, 2H), 7.05(AB, J=3.3, 4.2Hz, 2H), 6.91(d, J=1.1Hz, 2H), 6.78(dd, J= 3.0, 4.5Hz, 2H), 6.60(s, 2H), 5.48(m, 2H); 19 F NMR(282MHz, CDCl 3 /CFCl 3 ), two equal intensity AB quartets, -111.9 (d, J = 247.0 Hz) and -115.7 (d, J = 244.0 Hz), -117.79 (d, J = 240.8 Hz) and -119.54 (d, J = 240.8 Hz); MS (EI) 428 (M + ), 368, 252, 192, 176 and 57; 13 C NMR(126MHz, CDCl 3 ) 146.8, 141.8, 137.6, 134.1, 128.9, 128.8, 127.3, 126.3, 45.7; HRMS calcd for C 22 H 12 F 8 428.0811, found 428.0811. Anal. Calcd for C 22 H 12 F 8 : C, 61.69; H, 2.83. Found: C, 61.52; H, 2.69. Reaction of Aryne 1 with t-Butylbenzene. The procedure was identical to those above, except that the reaction was carried out using refluxing tert-butylbenzene (bp 169 ) as both a solvent and a reactant. The product was purified by silica gel chromatography (hexane/EtOAc, 100:1) with the yield of 6 being 78%: mp 131-133; 1 H NMR (500MHz, CDCl 3 /TMS) 7.28(d, J=8.4Hz, 1H), 7.24(d, J=8.4Hz, 1H), 7.06(m, 1H), 7.02(m, 1H), 6.97(d, J=8.7HzHz, 1H), 6.90(d, J=8.7Hz, 1H), 6.62(s, 2H), 6.19(d, J=6.2Hz, 1H), 5.49(d, J=5.6Hz, 1H), 5.39(m, 1H), 0.91(s, 9H); 19 F NMR (282MHz, CDCl 3 /CFCl 3 ), four equal intensity AB quartets at -111.4 (J = 243.9 Hz) and -112.5 (J = 243.9 Hz), -115.3 (J = 243.9 Hz) and -115.9 (J = 243.9 Hz), -117.2 (J = 240.8 Hz) and

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46 119.8 (J = 240.8 Hz), -118.4 (J = 241.1 Hz) and -119.4 (J = 240.8 Hz); 13 C NMR (126MHz, CDCl 3 ) 147.5, 147.3, 138.3, 137.4, 134.3, 133.9, 130.3, 129.0, 128.9, 128.6, 126.9, 126.6, 126.3, 126.2, 120.0, 46.8, 45.5, 34.7, 27.6; Anal. Calcd for C 26 H 20 F 8 : C, 64.46; H, 4.17. Found: C, 64.22; H, 4.22. Reaction of Aryne 1 with Naphthalene. The procedure was carried out as above except that di-n-butyl ether (bp 142) was used as the solvent and naphthalene as the substrate (0.14 g, 1.1 mmol). Refluxing for 30 min provided a mixture of products (ratio >10:1), which after chromatography in the usual manner gave major product endo-adduct 4 in a yield of 88%: mp 204-206; 1 H NMR (300MHz, CDCl 3 /TMS) 7.59(m, 2H), 7.27(m, 2H), 7.22(s, 2H), 6.93(m, 2H), 6.70(s, 2H), 5.78(s, 2H), 5.75(s, 2H); 13 C NMR (126MHz, CDCl 3 ) 145.2,143.3, 141.2, 133.9, 130.0, 128.8, 127.58, 127.0, 125.8, 125.3, 47.5; 19 F NMR(282MHz, CDCl 3 /CFCl 3 ), two equal intensity AB quartets, -111.2, -115.5 (J AB = 243.9 Hz), and -116.4, -119.5 (J AB = 247.0 Hz); HRMS calc 478.0967, found 478.0968. Anal. Calc for C 26 H 14 F 8 : C, 65.28; H, 2.95. Found: C, 65.05; H, 2.89. Minor product (presumably exo-adduct): 19 F NMR, two equal intensity AB quartets, -112.0, -115.3 (J AB = 246.8 Hz) and d -117.8, -119.6 (J AB = 236.9 Hz). Reaction of Aryne 1 with Furan. This reaction was carried out as above in refluxing tert-butylbenzene for 20 min with furan as the substrate. A mixture of the endo and the exo-adducts, 12a,b, (ratio = 1:0.6), was obtained in 80% yield. Chromatography in the usual manner provided partial separation of the isomers, such that small amounts of individual, pure isomers could be obtained, along with larger amounts of mutually contaminated fractions. endo-Isomer, 12a: mp 162-163.5; 1 H NMR (300MHz,

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47 CDCl 3 /TMS) isomer1 7.33(s, 2H), 7.22(s, 2H), 6.99(d, J=0.9Hz, 2H), 6.65(s, 2H), 5.91(d, J=3.9Hz, 2H); 13 C NMR (126MHz, CDCl 3 ) 150.4, 144.1, 134.8, 129.7, 129.2, 127.6, 127.3, 119.4, 118.9, 81.0; 19 F NMR(282MHz, CDCl 3 /CFCl 3 ), two equal intensity AB quartets, -112.6, -119.2 (J AB = 243.9 Hz), -116.1, -117.9 (J AB = 240.8 Hz); HRMS calcd for C 20 H 10 F 8 418.0604, found 418.0604. exo-Isomer, 12b: 1 H NMR (300MHz, CDCl 3 /TMS) 7.41(s, 2H), 7.29(s, 2H), 6.76(s, 2H), 6.51(s, 2H), 5.88(m, 2H); 13 C NMR (126MHz, CDCl 3 ) 147.5, 140.6, 134.2, 128.8, 128.5, 127.9, 127.7, 119.3, 118.7; 19 F NMR(282MHz, CDCl 3 /CFCl 3 ), two equal intensity AB quartets, -111.9, -114.3 (J AB = 243.9 Hz), -116.2, -118.0 (J AB = 238.0 Hz). Reaction of Aryne 1 with Bicyclo[2.2.1]hepta-2,5-diene: The procedure was carried out as above except that di-n-butyl ether (bp 142) was used as the solvent and bicyclo[2.2.1]hepta-2,5-diene (0.043g, 50ul, 0.46mmol) was used as the substrate (0.14 g, 1.1 mmol). A mixture of products (ratio15a:15b:16a:16b=62:27:3:8) was obtained after refluxing for 30 min. A product mixture (75 mg) was obtained in a total 67% yield after chromatography in the usual manner, which includes four different isomers: exoand endo-1,4-addition products 15a&b, endoand exo-1,2addition products 16a&b with a ratio of 62:27:3:8. Spectrum of 15a: 1 H NMR (500MHz, CDCl 3 /TMS) 7.27(s, 2H), 7.14(S, 2H), 6.80(s, 2H), 3.37(s, 2H), 3.05(s, 1H), 1.88(m, 1H), 1.81(m, 2H), 1.12(m, 2H); 13 C NMR(126MHz, CDCl 3 ) 149.9, 135.1, 130.0, 128.3, 127.9, 119.9, 119.1, 56.5, 47.0, 33.7, 23.8, 21.3; 15b: 1 H NMR (500MHz, CDCl 3 /TMS) 7.40(s, 2H), 7.02(s, 2H), 6.65(s, 2H), 3.40(s, 2H), 2.04(m, 1H), 1.88(m, 1H), 1.78(m, 1H), 1.66(s, 2H); 13 C NMR(126MHz, CDCl 3 ) 145.3, 134.5, 128.8, 128.8, 128.2, 127.8, 119.6, 118.8, 56.4,

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48 49.0, 31.0, 25.2, 19.9; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -110.5 (d, J=240.83Hz), -111.9 (d, J=240.83Hz), -112.79(d, J=241.11Hz), -114.09(d, J=247.03Hz), -114.98(d, J=237.73Hz), -115.04(d, J=240.83Hz), -115.15 (d, J=237.73Hz), -116.16 (d, J=238.0), -116.28 (d, J=241.11Hz), -116.99 (d, J=234.62Hz), -117.14 (d, J=240.83Hz), -117.18 (d, J=237.73Hz), -118.14 (d, J=237.73Hz), -117.35 (d, J=243.93Hz), -119.16 (d, J=238.0Hz), -119.69 (d, J=241.11Hz); 16a: 1 H NMR (500MHz, CDCl 3 /TMS) 7.56(s, 2H), 6.98(s, 2H), 6.62(s, 2H), 6.28(m, 2H), 3.17(s, 2H), 1.92(s, 1H), 1.81(m, 1H); 13 C NMR(126MHz, CDCl 3 ) 142.7, 136.9, 134.9, 131.1, 126.7, 128.6, 128.9, 126.7, 118.9, 118.6, 50.4, 42.8, 40.3; 16b: 1 H NMR (500MHz, CDCl 3 /TMS) 7.31(s, 2H), 7.23(s, 2H), 6.92(s, 2H), 6.31(m, 2H), 2.88(m, 2H), 2.86(m, 2H), 1.21(s, 1H), 0.73(m, 1H); 13 C NMR(126MHz, CDCl 3 ) 147.9, 137.1, 134.8, 129.8, 128.9, 128.5, 124.6, 118.4, 118.4, 46.6, 42.7, 41.4; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -111.42 (d, J=244.21Hz), -112.48 (d, J=243.93Hz), -115.31(d, J=244.21Hz), -115.92 (d, J=244.21Hz), -117.17 (d, J=240.55Hz), -118.35 (d, J=240.55Hz), -119.40 (d, J=240.26Hz), -119.81 (d, J=240.55Hz); MS(EI) m/z 442(M + )(3), 191(100), 176(63), 126(13). HRMS Calc. for C 23 H 14 F 8 442.0967, Found 442.0974 (EI). When pure bicyclo[2.2.1]hepta-2,5-diene is used as solvent and reactant, the ratio of 15a:15b:16a:16b is 74:12:10:4. Isomer 15a is separated from the others by chromatography and has a melting point of 233-235. Reaction of Aryne 1 with 1,4-Dimethylnaphthalene: The procedure was carried out as above except that 1,4-dimethylnaphthalene (0.10 g, 0.6mmol) was used as the substrate. A mixture of products (ratio 3.43:1) was obtained after refluxing for 30 min,

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49 which after chromatography in the usual manner gave major product endo-5,8-adduct 7 in a yield of 60%. Endoproduct: 1 H NMR (500MHz, CDCl 3 /TMS) 7.07(s, 2H), 6.86(s, 2H), 6.79(m, 2H), 6.51(s, 2H), 5.92(s, 2H), 5.65(s, 2H), 2.49(s, 6H); 13 C NMR(126MHz, CDCl 3 ) 145.4, 141.6, 141.4, 134.4, 131.3, 128.6, 128.6, 127.9, 127.5, 127.4, 120.4, 119.1, 43.9, 18.1; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -108.94, -114.22 (AB, J=243.93Hz, 4F), -114.76, -118.48 (AB, J=238.01, 4F); Exoproduct: 1 H NMR (500MHz, CDCl 3 /TMS) 7.13(s, 2H), 7.06(s, 2H), 6.91(s, 2H), 6.55(s, 2H), 6.54(s, 2H), 5.87(m, 2H), 2.23(s, 6H); 13 C NMR(126MHz, CDCl 3 ) 145.7, 143.6, 137.6, 137.5, 134.2, 130.1, 129.4, 129.0, 127.4, 126.5, 120.1, 119.0, 44.2, 18.1; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -111.86, -115.20 (AB, J=243.93Hz, 4F), -117.74, -119.21 (AB, J=240.83Hz, 4F); MS(EI) m/z 506(M + )(99), 330(100), 176(8); HRMS Calc. for C 28 H 18 F 8 506.1280, Found 506.1293 (EI). The stereochemistry was proven by the nOes between 2.49 and 5.65 in the major and between 7.06 and 6.91 in the minor. Reaction of Aryne 1 with 2,3-Dimethylnaphthalene: the procedure was carried out as above except that 2,3-dimethylnaphthalene (0.10 g, 0.6mmol) was used as the substrate. A sole endo product was obtained after refluxing for 30 min, which after chromatography in the usual manner gave major product endo-adduct 8 (85 mg) in a yield of 67%. Solid starts to decompose at 168. 1 H NMR (300MHz, CDCl 3 /TMS) 7.53 (m, 2H), 7.24(m, 2H), 7.17(d, J=1.2Hz, 2H), 6.67(s, 2H), 5.71(s, 2H), 5.27(d, J=1.8Hz, 2H), 1.71(s, 6H); 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -111.19, -114.90 (AB, J=243.93 Hz, 4F), -116.44, -119.42 (AB, J=237.73Hz, 4F); 13 C NMR(75MHz, CDCl 3 ) 144.9, 143.1, 141.2, 133.9, 128.9, 127.9, 127.6, 127.1, 125.7, 124.7, 120.0, 118.7, 53.5,

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50 16.5; MS(EI) m/z 506(M + )(77), 330(100), 176(14); HRMS Calc. for C 28 H 18 F 8 506.1280, found 506.1288 (EI). Reaction of Aryne 1 with 2-Methoxynaphthalene: the procedure was carried out as above except that 2-dimethoxylnaphthalene (0.11 g, 0.7mmol) was used as the substrate (0.14 g, 1.1 mmol). A product mixture of was obtained after refluxing for 30 min, which after chromatography in the usual manner gave three products. Isomer 9, 18%: 1 H NMR (300MHz, CDCl 3 /TMS) 7.44(dd, J=8.1, 2.1Hz, 1H), 7.20(S, 2H), 7.17(t, J=2.5Hz, 1H), 6.90(m, 2H), 6.73(dd, J=8.1, 2.4Hz, 1H), 6.66(s, 2H), 5.83(dd, J=9.3, 12.6Hz, 2H), 5.64(d, 4.8Hz, 2H), 3.86(s, 3H) 19 F NMR (CDCl 3 /CFCl 3 ) -111.20, -115.45(AB, J=243.9Hz, 2F), -111.27, -115.48(AB, J=245.4Hz, 2F), -116.23, -119.48(AB, J=237.7Hz), -116.35, -119.63(AB, J=242.5Hz, 2F) 13 C NMR (75MHz, CDCl 3 ) 157.98, 145.38, 145.28, 144.99, 141.75, 140.83, 135.31, 133.94, 128.74, 128.42, 128.10, 127.64, 127.44, 127.10, 126.17, 125.61, 125.44, 124.20, 123.19, 119.93, 118.65, 112.54, 109.64, 102.16, 55.92, 47.50, 46.53. MS(EI) m/z C 27 H 16 F 8 O 508(M + )(77), 332(71), 276(35), 176(100); HRMS Calc. for C 27 H 16 F 8 O 508.1073, Found 508.1075 (EI). Isomer 10, 4%: 1 H NMR (500MHz, CDCl 3 /TMS) 7.18(t, J=5.8Hz, 2H), 7.12(d, J=8.1Hz, 1H), 7.09(d, J=7.2Hz, 1H), 7.02(d, J=8.1Hz, 1H), 6.91(s, 2H), 6.76(d, J=2.4Hz, 1H), 6.60(s, 2H), 6.34(dd, J=8.0, 2.5Hz, 1H), 5.58(dt, J=6.6, 1.18Hz, 1H), 5.57(dt, J=6.01, 1.86Hz, 1H), 3.69(s, 3H); 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -111.98 (d, J=243.93Hz, 1F), -112.05 (d, J=243.93Hz, 1F), -115.37(d, J=243.93Hz, 1F) -115.22(d, J=243.93Hz, 1F), -116.8 (d, J=241.11Hz, 1F), -116.91(d, J=238.01Hz, 1F), -119.26(d, J=237.73Hz, 1F), -119.44(d, J=237.73Hz, 1F); 13 C NMR (126MHz, CDCl 3 ) 157.2, 146.9, 146.0, 145.4, 138.1, 137.4, 137.1, 127.8, 127.8, 127.5, 127.5, 134.1, 134.1, 129.3, 129.3, 128.9,

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51 128.9, 124.4, 111.2, 109.4, 55.8, 47.9, 46.9; MS(EI) m/z 508(M + )(100), 332(90), 176(18); HRMS Calc for C 27 H 16 F 8 O 508.1073, Found 508.1068 (EI). Isomer 11, 27%: 1 H NMR (300MHz, CDCl 3 /TMS) 7.65 (tt, J=6.9, 1.8Hz, 2H), 7.48(m, 2H), 7.17(s, 2H), 7.02(s, 2H), 5.75(dd, J=24.6, 8.7Hz, 2H), 5.40(s, 1H), 5.20(t, J=2.7Hz, 1H), 2.02, 2.29(AB, J=18.3, 2.7Hz, 2H). 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -111.67 (d, J=247.03Hz, 1F), -112.16 (d, J=247.03Hz, 1F), -114.68 (d, J=246.75Hz, 1F), -115.45(d, J=243.93Hz, 1F), -117.05 (d, J=238.0Hz, 1F), -117.22 (d, J=241.11Hz, 1F), -119.32(d, J=240.83Hz, 1F), -119.40(d, J=240.83Hz, 1F); 13 C NMR(75MHz, CDCl 3 ) 202.04, 142.0, 140.0, 135.7, 134.5, 134.3, 134.0, 133.6, 130.3, 130.0, 129.7, 129.0, 128.7, 128.2, 128.0, 127.9, 127.5, 125.79, 125.77, 123.7, 122.1, 119.7, 118.5, 59.2, 41.8, 37.9; MS(NBA-C3) m/z 495 [M+H] + (13), 452(17), 276(24); HRMS Calc for C 26 H 13 F 8 O (M+H) 495.0995, Found 495.1970 (NBA-C3). Reaction of Aryne 1 with 2,5-Diphenylbenzofuran: the procedure was carried out as above except that 2,5-diphenylbenzofuran (0.11 g, 0.5mmol) was used as the substrate. A product mixture (ratio exo: endo=84:16) was obtained after refluxing for 30 min, which after chromatography in the usual manner gave major product exo-adduct 13a and endo-adduct 13b in a yield of 71% and 14% respectively. Exo-product gets soft at 220-222 and decompose at temperature above 240, while endo-adduct decompose at 192. Exo-Isomer: 1 H NMR (500MHz, CDCl 3 /TMS) 7.85(m, 4H), 7.56(t, J=7.7Hz, 4H), 7.50(t, J=7.6Hz, 2H), 7.33(s, 2H), 7.25(s, 2H), 7.20(, s, 2H), 6.64(s, 2H); 13 C NMR(126MHz, CDCl 3 ) 152.6, 148.3, 135.0, 135.0, 130.2, 128.3, 128.3, 128.3, 127.7, 127.2, 127.2, 127.2, 119.1, 118.6, 94.7; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -113.18(d, J=250.13Hz, 2F), -114.19(d, J=249.85Hz, 2F), -116.73(d, J=243.93Hz, 2F), -120.70(d,

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52 J=243.93Hz, 2F); endo-Isomer: 1 H NMR (500MHz, CDCl 3 /TMS) 7.84(s, 4H), 7.54(m, 4H), 7.48(s, 2H), 7.43(m, 2H), 6.98(s, 2H), 6.60(s, 2H); 13 C NMR(126MHz, CDCl 3 ) 153.0, 142.7, 136.2, 133.7, 129.5, 128.8, 128.7, 128.4, 128.2, 128.0, 118.5, 118.2; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -106.25(d, J=238.01Hz, 2F), -109.26(d, J=237.73Hz, 2F), -114.60(d, J=234.91Hz, 2F), -118.96(d, J=234.62Hz, 2F); MS(EI) m/z 570(M + )(6), 176(3), 105(100); HRMS Calc for C32H18F8O 570.1230, Found 570.1239 (EI). Reaction of Bis-aryne 17 with Benzene: the analogous procedure was carried out by using 0.60 g (1 mmol) of the isomeric diiodides, 18a and 18b, and 1.12 g (10 mmol) of potassium t-butoxide. This mixture was refluxing in 10 mL of benzene for 2.5 h and product was purified by silica gel chromatography (hexane/EtOAc, 100:1) to give 0.42 g (83%) of the bis-adduct 19. Mp> 315; 1 H NMR (CDCl 3 /TMS) 6.98(m, 4H), 6.73(m, 4H), 6.22(s, 4H), 5.41(m, 4H); 13 C NMR (CDCl 3 /TMS) 146.8, 141.5, 138.0, 126.8, 124.6, 120.2, 45.6; 19 F NMR(282MHz, CDCl 3 /CFCl 3 ), one AB quartet, -110.9, -115.5 (J AB = 243.9 Hz); HRMS Calc for C 22 H 16 F 8 504.1124, found 504.1120. Reaction of Bis-aryne 17 with Naphthalene: The reaction was carried out as in the preceding example, except that the solvent was 10 mL of di-n-di-n-butyl ether, and 0.28 g (2.2 mmol) of naphthalene was added as the substrate. The mixture was refluxed at 142 for 30minutes. The residue was purified by silica gel chromatography (hexane/EtOAc, 100:1) to give 0.52 g (86%) of white solid, bis-adduct 20. Mp 253 (dec.); 1 H NMR (300MHz, CDCl 3 /TMS) 7.53(m, 4H), 7.20(m, 4H), 6.89(m, 4H), 5.69(m, 4H), 5.24(s, 4H); 13 C NMR (126MHz, CDCl 3 ) 145.3, 143.8, 140.9, 127.5, 125.6,

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53 124.9, 124.3, 120.0, 47.4; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ), one AB quartet, -108.9, -115.0 (J AB = 243.9 Hz); HRMS Calc 604.1437, found 604.1437. Anal. Calc for C 36 H 20 F 8 : C, 71.52; H, 3.33. Found: C, 71.10; H, 3.28. Reaction of Bis-aryne 17 with Anthracene: The procedure was the same as in the preceding examples, except that the reaction was carried out for 30 min at 169 in 10 mL of refluxing t-butyl benzene, using 0.39 g (2.2 mmol) of anthracene as a substrate. The product was purified by silica gel chromatography (hexane/EtOAc, 100:1) with 0.56 g (80%) of the bis-adduct, 21, being obtained: mp > 310; 1 H NMR (300MHz, CDCl 3 /TMS) 7.59(m, 2H), 7.29(m, 2H), 7.19(m, 2H), 6.38(m, 2H), 5.96(s, 2H), 5.37(s, 2H); 19 F NMR (282MHz, CDCl 3 /CFCl 3 ), one AB quartet, -109.1, -114.7 (J AB = 243.9 Hz); HRMS calcd for C 44 H 24 F 8 704.1744, found 704.1748. Reaction of Bis-aryne 17 with [2.2]Paracyclophane: The procedure was carried out in refluxing t-butylbenzene, as in the previous example, and 0.46 g (2.2 mmol) of [2,2]paracyclophane was used as a substrate. The crude product was purified by silica gel chromatography (hexane/EtOAc, 100:1), a 50:50 mixture of the diastereoisomeric bis-adducts 22a and 22b, 0.64 g (84%) white solid was obtained: mp 315 (dec.); 1 H NMR (300MHz, CDCl 3 /TMS) 7.03(d, J=7.8, 2H), 6.94(d, J=8.4Hz), 6.93(s, 4H), 6.05(d, J=8.4, 2H), 5.97(d, J=8.4Hz, 2H), 5.89(d, J=6.3Hz, 2H), 5.62(d, J=6.0Hz, 2H), 4.51(m, 2H), 4.44(m, 2H), 3.09(m, 2H), 2.99(m, 2H), 2.78(m, 4H), 2.54(m, 4H), 2.38(m, 2H), 2.23(m, 2H); 13 C NMR (126MHz, CDCl 3 ) 147.07, 142.51, 139.84, 139.62, 137.61, 134.63, 133.03, 128.05, 126.41, 126.08, 125.76, 125.37, 125.04, 124.37, 123.11, 51.59, 51.10, 34.66, 34.24, 33.64, 33.36; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) (isomer 1) two

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54 equal intensity AB quartets, -109.6, -115.0 (J AB = 243.9 Hz), -110.9, -115.6 (J AB = 240.8 Hz); (isomer 2) two equal intensity AB quartets, -109.7, -115.2 (J AB = 231.8 Hz), -110.6, -115.4 (J AB = 231.5 Hz); HRMS calcd for C 48 H 36 F 8 764.2689, found 764.2689.

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CHAPTER 3 CADOGAN METHOD AND REACTION MECHANISM 3.1 Introduction N-nitrosoacetanilide was also reported by Cadogan in 1972 to generate benzyne via decomposition of the intermediate benzene-diazonium salt. 102 103 The mechanism that he proposed is illustrated in Figure 3-1, and in this chapter we will describe the application of Cadogans method to the generation of AF4-yne. N O N O N N O O N N O O N NO N2 Ac2O ++ Figure 3-1 Decomposition of benzene-diazonium slat Aryne chemistry is very important in the synthesis of natural products and has been well reviewed. 66 Three main classes of reactions have been observed: a) Diels-Alder (DA) addition with 1,3-dienes; b) ene-reaction with alkene possessing a suitable allylic proton; c) 2+2 cycloaddition. 55

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56 The generation of an aryne by treatment of an aryl halide with potassium t-butoxide is first reported by Cram, and in this chapter we will describe this procedure as the Cram method. In his original study, aryne reactions were carried out in dimethyl sulfoxide, and the t-butoxide ion adduct was the major product. We have already discussed the 4, 5-dehydroand 4, 5, 15, 16-bis(dehydro)octafluoro [2,2] paracyclophane aryne reactions generated by potassium t-butoxide with the corresponding iododerivatives in Chapter 2. 49, 50 High yields of DA products were obtained using the Cram method. When the Cadogan method is applied to the same system, it will be seen that the two methods gave essentially the same results with regard to DA reactions. However, in the reaction of aryne with alkenes, the outcomes are totally different. The latter method gives ene products whereas the former method gives no ene reactions, but instead a reduced, octafluoro[2.2]paracyclophane (AF4) product. 3.2 Results and Discussion 3.2.1 The Cadogan Method Cadogan first reported decomposition of benzene diazonium salt to generate benzyne in situ in 1972. 102 Biphenyl was obtained in up to 80% yields in benzene solution (radical reaction), but giving 31% of ene products in a reaction with methyl methacrylate. 103 When this method is applied to the AF4 system, it gave results virtually identical to these obtained via the Cram method, when carried out in the presence of a diene trap, such as benzene, naphthalene or anthracene. For the Cadogan method, 90%, 93% and 95% yields of DA products were obtained for DA reactions with benzene, naphthalene and anthracene, respectly, as compared to 86%, 88%, 84% when using the Cram method. The ratios of product isomers varied a little bit. The ratio of anthracene

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57 adducts changed from 97:3 to 95:5, whereas the naphthalene product mixture contains 15-17% exo-adduct versus 8-10% when using the Cram method. 3.2.2 Ene Reactions When 4-iodo-octafluoro[2.2]paracyclophane (IAF4) was allowed to react with potassium t-butoxide and 1-octene in butyl ether or in pure 1-octene as solvent, only the reduced AF4 was observed. In contrast, AF4-yne generated from the decomposing of 4-(N-nitroso)-acetamide-octafluoro[2.2]paracyclophane (the Cadogan method) gave ene product 1 in 83% yield with only minor (5%) amount of reduced product AF4 (Figure 3-2). The critical step in the generation of aryne in the Cadogan method is the loss of the proton ortho to the diazonium group. The strong electron withdrawing fluorinated bridge groups make the proton more acidic and thus easier to lose, making the rate of aryne generation faster than the radical generation in the AF4 system. F2C CF2 HN O CF2 F2C F2C CF2 CF2 F2C Cl O O NO 1-Octene+butyl ether F2C CF2 N O CF2 F2C NO 1 Figure 3-2 1-Octene with AF4-yne reaction When cyclohexene and cylopentene were allowed to react with AF4-yne generated by the Cadogan method, ene products were obtained in 55% and 53% yields, respectively. The reaction of AF4 -yne with cyclopentene afforded a 5.6:1 mixture of diastereomers

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58 2a/2b (Figure 3-3), identified by NMR of the product mixture. The structural integrity of compound 2a was demonstrated by the H1-H1 and H1-C13 (one-bond and long-range) couplings seen in the DQCOSY, GHMQC and GHMBC spectra, correspondingly. Couplings of the three aliphatic carbons with both of the alkene protons revealed the cyclopentene moiety. The couplings of 4.23 with 127.8 and 146.5 and of 5.23 with 146.5 CF2 CF2 F2C CF2 119.8118.97.16130.3129.47.02118.9118.07.16130.37.08129.46.88127.37.08129.4127.86.92135.4146.5135.4135.4135.047.05.23135.05.65131.132.92.522.5230.32.152.52 H 4.232a CF2 CF2 F2C CF2 119.8118.97.17130.3129.47.04118.9118.07.16130.37.08129.46.88127.37.08129.4127.86.83135.4148.1135.4135.4135.047.61.152.2434.82.242.2431.9130.36.07136.15.86 H 4.152b CF2 CF2 F2C F2C 120.0119.0129.47.12129.47.03119.0119.07.12129.47.04129.46.93129.47.12132.6127.66.96135.4148.1134.6134.6135.438.13.711.101.8233.71.211.4319.91.941.9425.2132.16.07126.75.823a CF2 CF2 F2C CF2 120.0119.0129.47.09129.47.00119.0119.07.16129.47.06129.46.90129.47.09132.6127.66.98135.4146.4134.6134.6135.43.7138.65.09131.65.53127.61.982.0124.71.941.7522.21.842.1827.63bH H Figure 3-3 Chemical shifts of cyclopentene and cyclohexene products demonstrated the connection of the cyclopentene moiety to the AF4 frame. Similar couplings were seen between the protons and the carbons of the minor diastereomer. The assignment of the protons and carbons of the AF4 moiety in the major product was based

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59 on the H1-H1 and H1-C13 (one-bond and long-range) couplings and the nOes seen between the protons of one ring and the protons of another. No such assignments were possible for the minor product, due to the overlap with the signals of the major. The relative stereochemistry of the two compounds was assigned based on the nOes between the protons of the cyclopentene moiety and the protons on the phenyl rings. In the major, it is the aliphatic protons at 2.15 and 2.52 which display nOes with the protons at 6.92 and 7.16. The proton transto 4.23, at 2.15, displays an extra nOe with 7.02. Conversely, the proton at 5.86 in the minor displays nOes with the protons at 6.83, 7.17 and 7.04 (the weakest) which were assigned as in Figure 3-3, based on the nOes intensity and chemical shifts. A weaker nOe was seen between 4.23 and 6.92. All these nOes are consistent with the stereochemistry proposed by MM calculations, which indicate that in the lowest energy conformation the proton of the cyclopentene (4.23 and 4.15) is in the plane of the benzene ring and facing the closest CF2 group. The other conformation with the proton in the plane of the benzene ring is ca. 10 kJ/mol higher in energy. Similarly, cyclohexene products 3a and 3b were assigned as in Figure 3-3, but the ratio of two isomers was 1:1. Surprisingly, when AF4-yne was generated using the Cram method, no ene products were observed in the presence of 1-octene, or cyclohexene with the reduced product, AF4, being the only observable product. Even pure 1-octene just gave reduction to AF4 under the Cram conditions. The AF4-yne generated under Cadogan conditions reacted with -methylstyrene to give the DA adduct 5 (24%) and ene product 4 (37%) (Figure 3-4). Another minor

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60 product alcohol, 6 (4% yield) may arise from the oxidation of ene product during its purification. CF2 F2C F2C CF2 116.24.675.35126.37.29128.17.28127.57.28132.17.323.544.0839.0145.9140.6140.7132.7135.4118.86.91130.4118.97.09132.17.13130.27.02129.6134.67.22126.5129.46.87134.8118.8119.7 F F F F F F F F 7.78120.5 136.22.7720.5132.17.99123.5128.37.647.55125.98.17133.1129.8129.9130.0118.87.39129.87.24127.87.34128.86.47127.2127.16.13118.8119.77.23129.9129.8118.1 CF2 F2C F2C CF2 HO 7.27134.4128.47.32122.87.4927.91.8468.2138.53.4138.32.55135.67.35134.6131.2120.0119.87.71130.5130.76.85134.87.43128.97.25127.0133.6118.9118.76.82131.16.97131.7130.4456 Figure 3-4 Chemical shifts of products from the reaction of -methylstyrene with AF4-yne 3.2.3 2-Methoxynaphthalene Reaction 2-Methoxynaphthalene reacts with IAF4 and KO t Bu in butyl ether to produce products (Chapter 2), the ketone product deriving from hydrolysis of the enol ether during the reaction or purification. In contrast, when 2-methoxynaphthalene reacts with AF4-yne generated via the Cadogan method, the major product obtained from the mixture is anthraceno[2.2]paracyclophane (43%), which had been alternatively synthesized by the reaction of 3,6-dipyridinyl-1,2,4,5-tetrazine with the AF4-yne

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61 naphthalene adduct (chapter 4). DA reactions on both substituted and unsubstituted ring were also observed under Cadogans conditions (total yields are 12%). It must be assumed that the phenyl anthraceno[2.2]paracyclophane is derived from a retro DA reaction by losing the methoxyetheno group as showed in Figure 3-5. CF2 F2C F2C CF2 OCH3 CF2 CF2 F2C F2C retro DA Figure 3-5 Retro Diels-Alder reaction of 2-methoxynaphthalene adduct to phenyl anthraceno[2.2] paracyclophane 3.2.4 Tetracyclone Reaction Tetraphenylcyclopentadienone (tetracyclone) is an excellent diene trap in Diels-Alder reactions. 102 1,2,3,4-Tetraphenylnaphthalene (70%) was obtained by Cadogan when using tetracyclone to trap benzyne in his original report. In the case of AF4-yne, 83% yield of adduct was obtained (Figure 3-6). CF2 F2C F2C CF2 Ph Ph 7.45128.0133.5117.77.30131.7132.9117.8138.6138.6143.5139.7129.96.03127.16.646.89125.97.15126.67.35132.4131.16.80142.67.07132.36.95126.46.93127.47.09126.57.15127.1 Figure 3-6 Chemical shifts of tetracyclone with AF4-yne product

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62 The assignment of the protons on the phenyl rings of this adduct was accomplished based on the H1-H1 couplings seen in the DQCOSY spectrum. Both phenyl rings displayed non-equivalence of the ortho and meta positions, indicative of restricted rotation. A quick variable temperature run showed that the pairs 6.80 7.07 coalesced at 50 60 C, while the protons on the other ring displayed no broadening at 60 C. The assignment of the carbons on the phenyl ring, as well as of those adjacent to the ipso positions was done on the basis of the H1-C13 couplings, one-bond and long-range, seen in the GHMQC and GHMBC spectra, correspondingly. The NOESY spectrum at room temperature displayed a nOe between 7.45 and 7.30, which identified the protons on the same side of the paracyclophane. The assignment of the rest of the carbons followed from the H1-C13 couplings. The only other non-trivial nOe in the NOESY spectrum was 6.93-7.35. A ROESY spectrum was then run at -20 C, temperature at which all protons displayed sharp signals. The nOe between 7.30 and 6.80 (chemical shifts at room temperature) allowed the assignment of the faster rotating phenyl ring to position 1 on the naphthalene, and of the proton at 6.80 to the side exo to the cyclophane moiety. The nOe between 7.35 and 6.93 agrees with a MM calculation in Perch, in which the phenyls in positions 2 and 3 are on the side of the naphthalene ring towards the cyclophane, while the phenyls in positions 1 and 4 are on the opposite side. NOes of 7.07 with both 7.35 and 6.03, in conditions in which 6.80 does not display any nOe with protons on the other phenyl ring, agree with this model. 3.2.5 Norbornadiene Reactions As described in Chapter 2, the AF4-yne generated from IAF4 under Cram conditions, gave major [2+2+2] adducts instead of the major [2+2] products that were observed by Heaney 98 and Noble 99 in their studies of the reactions of halogenated

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63 benzyne with norbornadiene. Tabushi, et al. also reported the predominant [2+2] cycloaddition products in the reactions of norbornadiene and quadricyclane with benzyne, ratio of 73/27 and 67/33, respectively, compared to [2+2+2] products. 104 In the case of AF4-yne as generated from 4-(N-nitroso)AF4 acetamide (Cadogan method), 103 the major products formed with norbornadiene were the [2+2+2] products as listed in Table 3-1, but the preference was not so strong as under Cram conditions. Table 3-1 [2+2+2] to [2+2] products ratio of norbornadiene with AF4-yne method solvent Temperature() a Ratio(15a:15b:16a:16b) b Cram Butyl ether 142(160) 62:27:3:8 Cram norbornadiene 90(110) 74:12:10:4 Cadogan Butyl ether 90(110) 39:21:21:19 a. Temperature in the parenthesis is the oil bath value. b. see Chapter 2 3.2.6 Reaction with 1,3,5-Cycloheptatriene The reaction of cycloheptatriene with benzyne provided another illustrative example of novel benzyne chemistry. Initially, Tabushi et al. 104 claimed that cycloheptatriene underwent a [2+6] cycloaddition along with ene reaction (approximately 1:1 ratio) in its reaction with benzyne. It turned out that the product was a [2+2] instead of a [2+6] cycloadduct, as reported by Lombardo 105, 106 and Crews 107 shortly thereafter, with an overall yield in the reaction was about 25%. [2+4] Cycloadducts were not observed in these investigations. Tropone reacted with benzyne to give a predominant [2+4] cycloadduct under the same conditions. 106 The rationale is that tropone has a planar structure while that of cycloheptatriene is not planar. Surprisingly, AF4-yne generated from Cadogans method didnt yield any [2+2] cycloadduct. All observed products were derived from an initial ene reaction (yields of

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64 61%). The primary ene product then reacted with another AF4-yne, apparently via the norcaradiene tautomer to give bis-AF4 adducts endo8a and exo-8b (1:1) in 38% yields as showed in Figure 3-7. In contrast, the AF4-yne as generated from Crams method gave only reduced AF4 (31%) plus the t-butoxide ion adduct (51%) in the reaction with cycloheptatriene. Neither [2+2], [2+4] nor ene reactions were observed. Proton and carbon chemical shifts of the products are illustrated below. The sequence of protons in the contiguous coupling network of [4.1.0]-bicyclohepta-3-ene moiety was revealed by the DQCOSY experiment. The carbons to which these protons are bound were identified in the GHMQC spectrum. Proton-carbon couplings of ca. 165-175 Hz confirmed the methines of the cyclopropyl ring. The three carbons on the AF4 frames to which the [4.1.0]-bicyclohepta-3-ene moiety is attached (at ca. 140-145 ppm) have been identified by their cross-peaks in the GHMBC spectra to protons two or three bonds away. The carbons adjacent to them couple with the protons three bonds away, e.g., in the case of 8a, 2.54 couples with 126.5 and 131.4, 129.2 couples with 4.89, and 128.5 couples with 4.74. Three of these carbons, at 129.2, 128.5 and 131.4 are split as a triplet of ca. 30-35 Hz by the two fluorines two bonds away. The remaining protons and carbons on the para-phenylene moieties to which the [4.1.0]-bicyclohepta-3-ene moiety is attached were assigned on the basis of the couplings between protons and carbons three bonds away. The DQCOSY spectrum confirmed the large coupling between protons which are ortho and the small couplings between protons which are meta. The configuration of compounds 8a and 8b was established by nOes. In both 8a and 8b, the cyclopropyl protons adjacent to the AF4 display an nOe to the alkene protons

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65 FFFFFFFFFFFFFFFF FFFFFFFFFFFFFFFF 2.541.671.974.746.176.234.896.706.677.367.366.896.946.536.957.137.197.067.087.407.046.846.116.947.317.017.102.451.300.944.746.496.554.946.826.817.197.176.856.8426.424.425.0140.9125.836.636.9128.5129.1144.1143.8131.027.126.424.437.437.1132.1132.5143.6129.2118.6126.8126.5128.5118.6143.9126.5141.4131.4125.4117.4125.0126.9128.3128.3127.3126.6126.1128.4125.5128.6127.6129.0130.8127.6129.2125.4128.3128.6125.2127.6125.0117.6117.6118.6118.9133.1132.8130.8130.9118.2117.7133.1133.9117.6117.4117.4117.4117.4117.6118.2134.2133.9133.1133.1132.8133.98b8a FFFFFFFF FFFFFFFF 6.997.167.047.167.217.11126.8131.2117.9126.8126.7130.9118.4128.2127.5128.2126.7117.6117.6133.3134.0142.939.1116.2125.5129.4130.0123.2120.27.183.065.506.456.706.626.044.587.117.277.096.98117.57.09142.6139.3126.96.26120.15.4726.62.372.42122.15.49125.06.24133.46.539a9b Figure 3-7 Chemical shifts of cycloheptatriene products 8 and 9 (2.54 with 6.17 and 6.23; 2.45 with 6.49 and 6.55) while the other cyclopropyl protons do

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66 not, therefore the configuration of the [4.1.0]-bicyclohepta-3-ene moiety is endo in bothcompounds. In 8a, the cyclopropyl protons at 1.67 and 1.97 display an nOe with two aromatic protons at 6.89 and 6.94, while in 8b the alkene protons at 6.49 and 6.55 display nOes with the aromatic protons at 6.84 and 6.85, indicating that the addition of the [4.1.0]-bicyclohepta-1,3-diene yielded the endo product for 8a and the exo product for 8b. The relative size of these nOes allowed the assignment of the aromatic protons, i.e., the nOe of 1.67 with 6.89 was larger than the nOe of 1.67 with 6.94. The use of nOes in the assignment of the configuration of the AF4 unit bound to the cyclopropyl was based on the fact that the cyclopropyl proton to the AF4 (2.54 in 8a) is approximately in the plane of the para-phenylene and is facing the nearest CF2. This is the geometry found by a conformational search using MM2 in Hyperchem, and confirmed by the nOes displayed by the products of the reaction of the AF4 arene with cyclopentene and with cyclohexene [page 59]. In compound 8a, 1.97 displays nOes with two aromatic protons at 7.08 and 7.40, while 1.67 does not, therefore the other para-phenylene ring of the AF4 moiety bound to the cyclopropyl ring is on the same side of this ring as 1.97. Of 7.40 and 7.08, only the former displays an nOe with 2.54, therefore they are syn. Similar nOes were used in the case of 8b, to assign the protons at 7.31 and 7.04. Simple ene products 9a and 9b (2:1) as depicted in Figure 3-6 were also obtained in 23% yield, the latter deriving from 9a via subsequent 1,5-H shift. The GHMBC spectrum displayed couplings for 9a between the protons at 5.50 and 4.58 and the carbon at 142.9, and for 9b between the protons at 6.26 and 6.53 and the carbon at 142.6, which identified the carbon on the AF4 moiety to which the cycloheptatriene moiety is

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67 connected. Couplings between the protons and carbons of the methines at 39.1, 3.06 and at 126.8, 7.18 identified the methine ortho to 142.9 in 9a. A similar coupling between the proton at 7.09 and the carbon at 139.3 identified the proton ortho to 142.6 in 9b. Long-range couplings between the protons and carbons in a meta relationship were used to assign the chemical shifts on the AF4 moiety for 9a. In the case of the minor product 9b, these assignments could not be made because of severe overlap with the stronger peaks of 9a. The assignment of the protons on the cycloheptatriene moiety in 9a assumed a geometry in which the proton at 3.06 is in the plane of the para-phenylene and is facing the nearest CF 2 This is the geometry found by a conformational search using MM2 in Hyperchem, and confirmed by the nOes displayed by the products of the reaction of the AF4 arene with cyclopentene and with cyclohexene [page 59]. Two nOes, between 3.06 and 7.21 and between 5.50 and 7.11 allowed the assignment of the protons on the face of the other para-penylene moiety of the AF4, as 7.21 being syn to 3.06. 4.58 display a nOe with 7.18 only. The conformation of the cycloheptatriene ring in 9a is with the double bond having 6.62 and 6.70 folded toward 3.06, as demonstrated by nOes between 3.06 and these other two protons. In the case of 9b, both 6.26 and 6.53 display nOes with 7.27 and 7.09, as expected for little preference for one orientation or the other of the cycloheptatriene moiety. The most shielded proton at 7.27 was assigned as syn to the cycloheptatriene. The side endo to the AF4 displayed deshielding compared to the side exo in all of the compounds studied; therefore one can assume that the preferred conformation has the CH 2 of cycloheptatriene on the exo side of the AF4.

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68 Normally, cycloheptatriene undergoes DA reactions with most dienophiles via its valence tautomer, bicyclo[4.1.0]hepta-2,4-diene (norcaradiene) which is present in very small quantities in equilibrium with cycloheptatriene. 108, 109 With an extremely reactive reagent such as benzyne, the benzyne is apparently so reactive that it reacts preferentially with the major tautomer and there is simply too little norcaradiene present to lead to significant product. Why should the very reactive AF4-yne give rise to norcaradiene derived products (8a& 8b) when benzyne itself did not? It may be that the primary ene product, 7-AF4-substituted cycloheptatriene, has a much greater amount of its respective norcaradiene tautomer present in equilibrium, thus allowing AF4-yne to react with this tautomer in the preferred manner. Ciganek et al. found that substitutents containing systems would help the stabilization of the norcaradiene valence isomer. 110 AF4 system is quite electron deficient due to the two bridge fluorine substitutents, and importantly, AF4 moiety is quite bulky which will force the equilibrium to the side of norcaradiene tautomer. 109 AF4 H AF4 H AF4-yneDA products 8a & 8b Figure 3-8 Primary AF4-yne ene product with AF4-yne reaction to products 8a&8b Equilibrium of cycloheptatriene with norcaradiene has been extensively studied in 1960s and 1970s. No norcaradiene valence tautomer could be detected by variable-temperature 1 H NMR even down to -150. 111, 112 Only ca. 3% norcaradiene could be observed for 7-carboxyl acid substituted derivative at the above temperature. 113 With two acceptor substitutents at 7 position, for example, CN, the norcaradiene is the more stable form by ca. 6 kcal, 110, 114 whereas that of unsubstituted cycloheptatriene is the more

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69 stable form by ca. 11 kcal. 115, 116 Adam et al. 109 studied the cycloaddition of 7-substituted cycloheptatriene with singlet oxygen and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD), which is a very dienophilic reagent. He found that the product ratio with singlet oxygen follow the order CHO CO2Me CN > ph > H > MeO, the norcaradiene [2+4] adduct increase from the left to right, being exclusively norcaradiene adduct for MeO and exclusively cyclohetpatriene adduct for CHO, CO2Me and CN. For H mainly the former and for ph mainly the later are formed. In contrast, only the norcaradiene [2+4] adduct was produced for PTAD for all substituents. electron acceptor such as CN, CO2Me and CHO, stabilize the cyclopropane ring by decreasing the antibonding C1-C6 electron density, while the effect is reversed for donor MeO. His rationale for the abnormal product for PTAD is that the cycloaddition activation energy for cycloheptatriene is much high than that of norcaradiene, 17-20 kcal/mol, lie well beyond the equilibrium activation energy, 2-12kcal/mol. Comparing with the singlet oxygen, PTAD is much more slower and more selective with in its dienophilic reaction with cycloheptatriene. Similarly, AF4-yne is quite bulky and reactive intermediate, the cycloaddition activation energy must be very high for cycloheptatriene due to the steric issue, while that for norcaradiene is much lower and faster reaction. On the other hand, AF4 moiety is electron deficient acceptor, the equilibrium of 7-AF4-cycloheptatriene would favor the 7-AF4-norcaradiene, which in turn would increase the reaction rate of norcaradiene with AF4-yne. 3.3 Mechanistic Study of AF4-yne The parent benzyne and eventually all 1,2-arynes have singlet ground state, with o-benzyne itself having a singlet-triplet energy gap of 37.5 kcalmol -1 57, 117 Since arynes are

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70 simple strained alkynes, the Woodward-Hoffmann rules do not permit a concerted superafacial (S) 2S+2S thermal cycloaddition. On the other hand, [2+4] cycloadditions should be concerted, stereospecific reactions. Dienes generally undergo [2+4] cycloadditions with arynes, but when the diene system is sufficiently distorted from planarity, step wise [2+2] cycloaddition with benzyne becomes energetically feasible. 107 3.3.1 Base and Solvent Study Arynes are also very reactive towards nucleophilic addition. 66, 118-120 There is a question therefore regarding why there is no t-butoxide ion adduct formed in the AF4-yne reactions, in contrast to that Cram originally reported with his benzyne study. 24 Base and solvent effects in this AF4-yne system were investigated (Table 3-2). A striking observation is that no DA reaction with anthracene is observed when sodium t-butoxide is used instead of potassium t-butoxide. After refluxing in butyl ether for two hours, most starting material remains. Sodium amide, which is a strong and commonly used base for aryne generation, 70, 121-123 also gives no anthracene adduct in butyl ether (of course, it may be destroyed by butyl ether). Reduced product AF4 plus 5% DA products with some starting material were observed when refluxing in t-butylbenzene for two hours in the reaction of IAF4 with NaO t Bu. In the polar solvent DMF, sodium amide simply reduces IAF4 to AF4 in over 90% yield. Table 3-2 Base and solvent effects in AF4-yne reaction with anthracene Solvent Base Temperature () Time (min) Diels-Alder adduct % (from the 19 F spectrum) t-butylbenzene KOBu t 169 30 83 Butyl ether KOBu t 142 30 82 Butyl ether NaOBu t 142 120 SM t-butylbenzene NaOBu t 169 60 IAF4:AF4:DA

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71 9.24:1:1.27 Butyl ether NaNH 2 142 120 Starting Material t-butylbenzene NaNH 2 169 270 IAF4:AF4:DA 2.70:1.21:1 Butyl ether NaHMDS Room 18h Starting material DMF NaNH 2 Room 18h AF4 (90%) DMF: dimethylformamide; HMDS: 1,1,1,3,3,3-hexamethyldisilazane; DA: Diels-Alder adduct. Why is the same base with different cations so different in the aryne generation? Sodium t-butoxide works better than sodium amide and potassium t-butoxide in the formation of t-butyl hypoiodite in cyclohexane by Wirth. 124 The solubility played an important role in that reaction system. Thus, the solubility of sodium and potassium t-butoxide in butyl ether was examined (Table 3-3). Table 3-3 Base solubility in butyl ether solvent Base Refluxing time solubility NaO t Bu (0.1132g) 5 min in 14 ml Clear solution KO t Bu (0.1123g) 30 min in 64 ml Most solid remains It is obvious that sodium t-butoxide has much better solubility in butyl ether than potassium t-butoxide does. A heterogeneous reaction system makes the base stronger! The dehydrogenation probably occurs on the surface of the strong base. The lack of reaction with sodium amide might be due to its limited surface area (pellets). In the reaction of IAF4 with sodium amide in t-butylbenzene, only 20% DA product was observed, whereas 100% of the starting material is recovered in butyl ether (Table 3-3). 3.3.2 The Different Selectivity of the Two Methods Why does the same aryne generated by different methods have such a huge difference in reactivity towards the same substrates? AF4-yne generated via the Cadogan method gave ene products in the presence of alkene, whereas only reduced AF4 was

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72 observed from the AF4-yne generated by the Cram method for the same type of reaction. The selectivity of arynes towards different substrates was examined first. Anthracene is such an excellent diene trap that the difference of speed of aryne generation may not be discerned between two methods. Therefore, naphthalene and benzene were first used as the diene trap in the competition experiments between Cadogan and Cram methods. Two methods selectivity towards benzene and naphthalene are listed in Table 3-4. Both methods show that naphthalene reacts much faster as the benzyne trap, which is consistent with earlier reports. 87, 88 The selectivities of naphthalene to benzene in Cadogan and Cram method are 512:1 and 285:1, respectively. Anthracene is the one of the most reactive diene trap in benzyne chemistry, but its actual selectivity versus benzene and naphthalene was not available. The competition between anthracene and naphthalene in DA reaction was carried out under Cram conditions, and the result was summarized in Table 3-5. In order to compare the result between Cram and Cadogan methods, some reactions were carried out in butyl ether at 110, which are the typical conditions for Cadogan method. Table 3-4 Competition reactions of naphthalene to benzene method substrate Time (min) Product ratio selectivity Cram Ben:Naph=1:1 30 Naph adduct 100% Cram Ben:Naph=112:1 180 Naph:Ben 74:26 Naph:Ben=307:1 Cram Ben:naph=169:1 180 Naph:Ben 63:37 Naph:Ben=287:1 Cram Ben:naph=449:1 180 Naph:Ben 37:63 Naph:Ben=260:1 Cadogan Ben:naph=63:1 Over night Naph:Ben 84:16 Naph:Ben=332:1 Cadogan Ben:naph=215:1 Over night Naph:Ben 76:24 Naph:Ben=688:1 Cadogan Ben:naph=493:1 Over night Naph:Ben 54:46 Naph:Ben=516:1

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73 Cram 1,4-dimethylnaph 20 Endo:exo 80:20 Adduct on non substituted ring Cadogan 1,4-dimethylnaph Over night Endo:exo 65:35 Adduct on non substituted ring Cram 2,3-dimethylnaph 30 Endo Adduct on substituted ring Cadogan 2,3-diemthylnaph Over night endo Adduct on substituted ring Cram 2-methoxynaph 30 3 adducts endo major Adduct on substituted ring Cadogan 2-methoxynaph Over night different product Adduct on substituted ring Reactions were run at 110 in butyl ether. Naph=naphthalene; Ben=benzene; DA=Diels-Adler. Table 3-5 Selectivity in Diels-Alder reaction under Cram conditions substrates Temp () DA adduct ratio selectivity Anth:Naph=1:10 142(reflux) Anth:Naph=73:27 Anth:Naph=26:1 Anth:Naph=1:10 110 Anth:Naph=75:25 Anth:Naph=30:1 Naph:Ben=1:50 110 Naph:Ben=80:20 Naph:Ben=200:1 When temperature is lower, AF4-yne has better selectivity to anthracene over naphthalene, 30/1 at 110 compared to 26/1 at 142. While the selectivity to naphthalene over benzene is 200/1 under Cram conditions compared to 512/1 under Cadogan conditions, which shows that AF4-yne generated under Cadogan conditions has better selectivity. We can deduce that selectivity to anthracene over benzene is 6000/1 under Cram conditions. Benzene is stable and the worst diene trap in benzyne DA reactions, 87 which is also obvious from the competition results above. The competition reaction of benzene with 1-octene (Table 3-6) gave only ene product under Cadogan conditions. When the same reaction was carried out under Cram conditions, reduced AF4 was the sole product with a large excess of 1-octene. t-Butoxide ion addition product was the major product along

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74 with reduced AF4 (former: AF4=1.5:1) if only 1.2 equivalents of 1-octene is used. Normally, t-butoxide adduct is not observed under Cram conditions. Table 3-6 Competition reactions of benzene to 1-octene method substrate Time(min) results Cram Ben:1-octene=1:1 5 hrs AF4:DA:other=32:2:46 Cram Ben:1-octene=1:4 5hrs AF4:DA:other=76:4:20 Cram Ben:1-octene=1:45 5 hrs AF4 Cadogan Ben:1-octene=1:1 Over night Ene product Reactions were run at 110 in butyl ether. Ben=benzene; DA=Diels-Adler; other=t-butoxide ion adduct. 3.3.3 The Selectivity of AF4-yne Toward Diels-Alder and Ene reaction Benzene is apparently not fast enough to capture all the AF4-yne when it is formed under Cram condition, thus, the above results could not provide the right information on the degree of aryne formation. Thus, anthracene was used as the diene trap in competition reactions with 1-octene. We assume that all the arynes were trapped by anthracene as soon as arynes were formed. The result is showed in Table 3-7. Table 3-7 Competition reaction of anthracene with 1-octene in butyl ether for 5 hours at 110under Cram condition Ratio(anthracene/1-octene) Results (DA products/AF4) 1:1 100 1:10 82:18 1:40 55:45 1:100 30:70 The data shows explicitly that aryne was formed even with 100 equivalents excess of 1-octene. So why was no ene reaction observed under Cram condition? The reduction rate of IAF4 to AF4 increases as the concentration of 1-octene increases. But this is not the case in norbornadiene reactions. The reactions of other alkenes with AF4-yne under Cram condition were summarized in Table 3-8. The amount of reduced AF4 increases as

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75 the amount of olefins increases, which means that olefin does have some effect in the reduction of AF4-yne. Table 3-8 Reaction of AF4-yne with olefins in butyl ether Method Substrate (equiv.) Conditions Results Cadogan 1-octene(2) 110 83% ene products Cram 1-octene(2) 110 3h 26%AF4 + 74% other a Cram 1-octene(10) 110 3h 64%AF4 + 36% other a Cram Cycloheptatriene(4) 120 5h 31%AF4 + 50% other a Cram Pure 1-octene Reflux 3h >90% AF4 Cadogan Cyclohexene(2) 110 55% ene products Cram 1-hexene(2) 110 3h 22%AF4 + 76% other a Cram 1-hexene(40) 110 6h >90%AF4 Cram t-butylethylene (2) 110 5h 42% AF4 + 57% other b Cram t-butylethylene(100) anthracene(1) 110 5h IAF4:AF4:DA 64:11:25 a: t-butoxide adduct; b: 2+2 cycloadduct Is AF4-yne formed under Cadogan conditions? Ene product was the only observable one when benzene and 1-octene were presented in a 1:1 ratio (Table 3-6). Is there any special selectivity toward ene reaction under Cadogan condition? Competition of ene with DA reaction was investigated and summarized in Table 3-9. Table 3-9 The AF4-yne selectivity of DA over Ene reaction under Cadogan conditions (3 h at 110 in butyl ether) substrates Products ratio (DA:Ene) Selectivity (DA/ene) Benzene:1-octene 1:1 Ene -Benzene:1-octene 40:1 19:81 1/139 Anthracene:1-octene 1:10 96:4 197/1

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76 Naphthalene:1-octene 1:1 69:31 2/1 The DA reaction of anthracene with AF4-yne is 197 times faster than ene reaction of AF4-yne with 1-octene, while that is just 2 times faster with naphthalene as diene trap in competition with ene reaction. It is very clear that benzene is much poorer diene trap than anthracene and naphthalene. Anthracene is 2.7*10 4 faster in DA reaction than benzene, which is consistent with the very poor yields for the DA reaction of benzene with some benzynes. Looking back at Table 3-4 and Table 3-5, we found that anthracene was more reactive than naphthalene and benzene by 30 times and 6000 times respectively under Cram conditions. The same relative reactivities are 98 and 2.7*10 4 toward naphthalene and benzene respectively under Cadogan conditions. The reason for the significant difference is not clear. To keep in mind that the former reactivity measurement was based on competition of DA reactions, whereas the latter one was based on the DA vs ene reactions. 3.3.4 t-Butoxide Ion Adduct One of the control experiments of IAF with KO t Bu and anthracene was carried out in butyl ether, with 100 equivalents of t-butylethylene added to the reaction mixture. After stirring at 110 for 6 hours, 11% reduced AF4 and 25% anthracene adduct were obtained with 64% starting material remaining. The slower rate may due to the lower boiling point of t-butylethylene (bp 41). When the alkene concentration was low, t-butoxide ion adduct was observed predominantly and this product decreases as the olefin concentration increases. Table 3-10 summarizes the results where the t-butoxide ion

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77 adduct was observed. Cycloheptatriene with AF4-yne under Crams conditions give 50% t-butoxide ion adduct with 31% AF4, acting as a normal alkene in this case. Table 3-10 Summary of t-butoxide adduct under Crams conditions reaction Yield of t-butoxide adduct (5) Benzene+1-octene (1:1) 46 Benzene+1-octene (4:4) 20 1-octene (2) 74 1-octene(10) 36 1-hexene(2) 76 Cycloheptatriene(4) 50 50% of t-Butoxide ion adduct was obtained with 31% AF4 in the reaction of cycloheptatriene with AF4-yne generated under Cram conditions, whereas 61% ene reaction product was observed under Cadogan conditions. 1-Hexene works the same way as 1-octene does to give 76% t-butoxide ion adduct if 2 equivalents 1-hexene is used. 3.3.5 Mechanism What is the difference between these olefins? Norbornadiene, a reactive olefin, gave mainly [2+2+2] cycloadducts under Crams conditions, whereas other alkenes do not give adducts. Was AF4-yne reduced by alkenes through electron transfer mechanism? The ionization potential of some alkenes is listed in Table 3-11. Electrons in the norbornadiene double bonds are delocalized due to the strain induced overlap. The bond order for the carbon-carbon bonds calculated by Brunger et al is 1.90 for the double bonds and 0.924 for the single bonds in norbornadiene, respectively. 125 The ionization potential of norbornadiene is 8.69 -8.73 eV, which is nearly 1 eV lower that of 1-octene.

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78 The energy level of electrons becomes higher as the substitutents on the double bond increase. It is interesting that the ionization potential of benzyne is 9.75 eV, much higher than most olefins. IAF4 is reduced by 1-octene but not by norbornadiene (chapter 2), thus, the reduction of AF4-yne by electron transfer from the olefin can be excluded from consideration. Iodide is a good leaving group and the fluorinated bridges provide the strong electron-withdrawing groups in the AF4 molecule. Therefore it should be possible to reduce IAF4 to AF4 directly. It has been found that alkyl halides undergo substitution reactions by the electron transfer, or S RN 1 mechanism. 127, 128 In the study of perfluoroalkyl iodides, which can not undergo S N 1 or S N 2 substitution with nucleophiles, Chen at al found that perfluoroalkyl iodide can be substituted by a S RN 1 type reaction very easily. 129, 130 Perfluoroalkyl halides can also be reduced by a S RN 1 mechanism. 131 Iodide ion was released in 68% yield after 30 min in the reaction of iodobenzene with potassium pinacolone enolate in the dark, while bromo-derivative was much less reactive under the same conditions. 132 Costentin at al reported thermal type S RN 1 reaction with 4-nitrocumyl chloride and 2-nitropropanate ion, which underwent either concerted or stepwise dissociation of C-Cl bond depending on the properties of the nucleophile. 133 Table 3-11 Ionization potential of alkenes 126 alkene ionization potential (eV) norbornadiene 8.69-8.73 (PE) propene 9.70-10.2(PE), 9.73(PI) 1-butene 9.62-9.77(PE), 9.59(PI) cyclohexene 9.11-9.12(PE), 8.94(PI)

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79 t-butylethylene 9.45(PE) 1-octene 9.60(PE), 9.427(PI) cis-2-octene 9.10(PE), 8.913(PI) benzene 9.2-9.25(PE), 9.20-9.27(EI) fluorobenzene 9.11-9.37(PE), 9.75(PI) ,,-trifluorobenzene 9.68(PE) benzyne(1,3-cyclohexadien-5-yne) 9.75(EI) *PE, photoelectron spectroscopy; PI, photoionization; EI, electron impact. Potassium t-butoxide could act as electron donor and could potentially reduce IAF4 via a S RN 1 mechanism (Figure 3-9). After the first electron transfer from the base, the AF4 radical could be obtained through dissociation of IAF4 radical anion. The radical could either accept another electron to become an anion and be protonated to form AF4 from there, or it could react with t-butoxide ion to get another radical anion (S RN 1 reaction). The latter radical anion could then transfer an electron to another IAF4 and produce t-butoxide ion adduct and close the free radical chain circle. The t-butoxide ion adduct was observed in the reactions where the olefin concentration was not high (Table 3-9). When the concentration of alkenes was high (>10eqiv.), the reduction from the AF4 radical directly must be predominant process.

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80 F F F F F F F F electron transfer(CH3)3CO F F F F F F F F ET F F F F F F F F OC(CH3)3 F F F F F F F F RH (CH3)3COK (5) F F F F F F F F I F F F F F F F F H butyl ether110oC, 3hI +I (CH3)3CO IAF4 F F F F F F F F OC(CH3)3 Figure 3-9 S RN 1 reduction of IAF4 to AF4 From Table 3-7, the AF4-yne was formed during the reaction process even with 100 equivalents of 1-octene. Thus, AF4-yne must be generated with or without any diene trap inside. If there was no substrate, reduced AF4 was observed with over 90% yields in the reaction of IAF4 with KO t Bu in butyl ether (Table 3-7). Therefore, a reduction mechanism was proposed depending on the information above (Figure 3-10). After the first electron transfer, radical anion was formed, which would grab proton from the surrounding to generate the AF4 radical. The AF4 radical could be further reduced by another electron transfer or attacked by t-butoxide ion to produce another radical anion and close the mechanism circle. Since no t-butoxide ion adduct was observed in the

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81 absence of olefin, the AF4 radical was reduced by second electron transfer to produce AF4. F F F F F F F F electron transfer(CH3)3CO F F F F F F F F F F F F F F F F H ET F F F F F F F F OC(CH3)3 H F F F F F F F F H RHRH (CH3)3COK (5) F F F F F F F F I 1-octene F F F F F F F F H butyl ether110oC, 3h+(CH3)3CO F F F F F F F F OC(CH3)3 H electron Figure 3-10 Reduction mechanism of IAF to AF4 in the presence of olefin Olefin in the reaction mixture may act as phase transfer reagent toward t-butoxide ion to increase the solubility of t-butoxide ion in butyl ether by forming a complex (Figure 3-11) which would make the t-butoxide ion attack on the AF4 radical more feasible to generate the t-butoxide ion adduct. When the concentration of olefin became much higher, solution became electron rich and olefin accelerated the electron transfer process.

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82 nKO Figure 3-11 Olefin with KO t Bu complex 3.3.6 Isotopic Labeling Experiments Isotopic labeling experiments were carried out to examine the mechanism. The reaction of IAF4 with KO t Bu was much slower in the presence of equal amount of t-butyl alcohol (Table 3-12). Alcohol increased the solubility of KO t Bu and made the base weaker. The NMR spectrum found deuterium incorporation in the reduced product of IAF4 with KOBu t /DO t Bu without a diene trap. The MS also showed fragment of 176(100), 177(53), 352(14), and 353(14), which meant about half of the reduced AF4 (38%) was deuterated. Deuterium exchange was also observed in this reaction. Recovered starting material IAF4 (22%) showed a peak at 479(5), 478(3), the isotopic ratio was much higher than that in pure IAF4 with MS peaks of 479(6) and 478(60). As expected, 44% DA products were observed in the presence of 1 equivalent of anthracene in the above reaction. AF4 was obtained in 52% and 40% yields in the reactions of AF4-yne with acetonitrile and N,N-dimthylformamide (DMF) as solvents, respectively. Dideuterated AF4 was observed in the reaction of IAF4 with KO t Bu in CD 3 CN in a ratio 1:1 with respect to the mono-deuterated AF4. The MS spectrum showed peaks at 354(19), 353(31), 353(12), 352(9) and fragments 178(54), 177(54), 177(35), 176(100) respectively, which meant that half of the AF4 obtained the second proton from the surrounding or moist during the workup. The formation of dideuterium substituted AF4 may indicate

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83 that the AF4-yne was formed and then reduced during the reaction course. The peaks of 353(12) and 177(35) came from the natural 13 C isotope of carbon. Table 3-12 IAF4 reduced to AF4 in refluxing butyl ether a Reaction Time (min) Result (AF4) IAF4 + KOBu t (5) b 30 >90% IAF4 + anthracene+ KOBu t (5) + HOBu t (5) 300 31% + 44% DA + other products c IAF4 + KOBu t (5) + HOBu t (5) 300 47% + other products c IAF4 + KOBu t (5) + DOBu t (5) 300 50.6% +other products c IAF4 + KOBu t (5) + acetonitrile 30 AF4 (33%)+ ring opening IAF4 + KOBu t (5) + DMF 30 AF4 (40%) + unknown a Default solvent unless mentioned separately; b In the parenthesis is the equivalent used; c the other products are ether adduct to AF4-yne. DA: Diels-Alder adduct. The reaction of IAF4 with KO t Bu in 1,1,1,1-tetradeuterobutyl ether was also investigated and was much slower than the same reaction in the non deuterated ether. After refluxing overnight, most starting material remained. This may due to the 1,1,1,1-tetradeuterobutyl ether is not pure enough or some alcohol is inside, which would make reaction much slower. 3.3.7 Reactions in the Presence of Electron Trap Reagents p-Dinitrobenzene (p-DNB) was used as electron trap reagents for verifying the S RN 1 mechanism, 132, 134 and p-DNB suppressed the electron transfer process in the radical nucleophilic substitution of perfluoroalkyl iodide. 130 The additive experiments were carried out to test our proposal, and results are listed in Table 3-13.

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84 Table 3-13 Additive effect on the reduction of AF4-yne with 1-octene under Cram conditions at 110 for 3 h Additive Results (ratio) AF4:IAF4:t-butoxide adduct p-DNB (2) 45:55:0 p-DNB (0.2) 31:0:69 Nitrobenzene (4) 38:62:0 Nitrobenzene (2) 54:25:21 Nitrobenzene (1) 62:14:24 Nitrobenzene (0.5) 59:0:41 However, no ene product is observed by adding either p-DNB or nitrobenzene. Nevertheless, these two additives did have effect on the reaction of IAF4; the reaction rate is much slower with 1 equivalent of nitrobenzene, 14% IAF4 remains after stirring at 110 for 3 h in butyl ether. The amount of starting material increased as the amount of nitrobenzene or p-DNB increased. 45% Reduced AF4 was detected by 19 F NMR from the crude reaction mixture along with 55% of starting material after 3 h at 110with 2 equivalents of p-DNB, while that was 25% with 2 equivalents of nitrobenzene. The t-butoxide ion product decreased as the amount of additive increased. There was no difference compared to the reaction of IAF4 with 1-octene under Cram conditions without any additive (Table 3-6) if only 0.2 equivalent of p-DNB or 0.5 equivalents of nitrobenzene was added. In Scamehorns study of halobenzene reactions, 132 p-DNB gave substantial electron trapping effect, while the nitrobenzene only had limited inhibition at the beginning, and then was followed by an increasing reaction rate. It seems that nitrobenzene is not as effective as p-DNB is, but they both work the same way in this

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85 system. Excess of p-DNB or nitrobenzene might change the entire reaction course due to nitrogroup strong electron withdrawing capability, while it was consumed quickly by the t-butoxide ion and had limited impact with limited amount. Table 3-14 Additive effect on the reaction of AF4-yne with anthracene under Cram conditions at 110 for 3 h Additive Result (AF4:IAF4:DA adduct) Nitrobenzene (1) 5:0:95 Nitrobenzene (4) 11:5:84 Nitrobenzene (4) + 1-ocetne (2) 10:30:60 p-DNB (2) +1-octene (2) 38:17:45 Similarly, the addictive effects on the DA reaction were carried out with anthracene as substrate (Table 3-14). Large amount of nitrobenzene (4 equiv.) would increase the amount of reduced AF4 to 11% along with 5% starting material from 5% AF4 and no starting material in the presence of 1 equivalent of nitrobenzene. The addition of 1-octene did have effect on the formation of AF4-yne. 30% of starting material remained in the same reaction with of 2 equiv. of 1-octene inside and the DA adduct decreased to 60% from 80% in the absence of 1-octene. While replacing the nitrobenzene with p-DNB, the amount of AF4 simply increased to 38%, which meant that p-DNB had more effect on the reduction of IAF4 or AF4-yne to AF4. 3.4 Conclusion A different method of generating AF4-yne in situ from N-(nitroso)-AF4 acetamide was discussed (Cadogan method), which gave the same results as Cram method in DA reactions, but a totally different outcome in the reactions with alkenes. Unusual ene reaction preference was observed in the reaction of AF4-yne generated by Cadogan

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86 method in the presence of benzene. The relative reactivity of different diene traps toward AF4-yne in DA reactions was established for the first time. Anthracene is 2.7*10 4 times more reactive than benzene referring to the AF4-yne ene reaction with 1-octene under Cadogan conditions, which, in turn, was faster than the DA reaction of AF4-yne with benzene by 139 times. The reaction of aryne with norbornadiene gave [2+2+2] products as the major one under Crams conditions, while almost equal amount of [2+2] and [2+2+2] products were obtained under Cadogan conditions. No [2+2] product was obtained in the reactions of AF4-yne with cycloheptatriene under Cadogan conditions, contrary to expectations based on the literature. All these results gave indication of the unique properties of the AF4-yne that was generated from N-(nitroso)-AF4 acetamide under Cadogan conditions. The anthracene versus 1-octene competition study under Cram conditions explicitly demonstrated that AF4-yne was formed even in the presence of 100 equiv. of 1-octene. This was further proved by the isotopic experiment of IAF4 with KO t Bu in DO t Bu and deuterated acetonitrile, where deuterated IAF4 and dideuterated AF4 were obtained, respectively. A reduction mechanism was proposed for the reduction of AF4-yne generated under Cram conditions. 1-Octene also had effect on the formation rate of AF4-yne. Alkenes increased the solubility of t-butoxide ion in butyl ether when theirs concentration was low, whereas olefin helped the electron transfer process and reduced the AF4 radical to AF4 directly when the concentration of olefin became much higher (>10 equiv.). It was possible that both mechanisms (direct reduction of IAF4 to AF4 or via AF4-yne) worked together depending on the amount of 1-octene present, i.e., the reduction from AF4-yne

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87 playing the major role in the absence of 1-octene, whereas AF4 reduction from IAF4 by S RN 1 increased as the concentration of 1-octene increased. The nitrobenzene or p-DNB, which is well known electron trap for S RN 1 reactions, slowed down the reaction of IAF4 with KO t Bu and increased the reduction rate of IAF4 to AF4 or via AF4-yne, which could be considered as evidence of the reduction of IAF4 or AF4-yne to AF4 by an electron transfer mechanism. Ene reactions were not fast enough to trap the AF4-yne generated under Cram conditions, which are harsh, with reduction by base ion by electron transfer process to AF4 directly. 3.5 Experimental General Methods. 1 H (500 MHz), 13 C (126 MHz), and 19 F (282 MHz) NMR spectra were recorded using CDCl 3 as the solvent, and chemical shifts ( values) were measured relative to the signals for CHCl 3 CDCl 3 and CFCl 3 respectively. 1 H and 13 C chemical shift data are directly indicated on the structures of the adducts in the Results and Discussion section above, whereas 19 F NMR data are provided in the Experimental Section below. X-ray crystal analyses were performed by the Center for X-ray Crystallography and HRMS and CH micro elemental analyses by the Spectroscopic Services Group at the University of Florida. Column chromatography was performed using chromatographic silica gel, 200-425 mesh, as purchased from Fisher, unless otherwise mentioned. All the competition reactions were carried out in the same way as the model reactions. The equivalents of reactants are displayed in the tables. One typical experiment of benzene with 1-octene is listed below. Benzene and 1-octene with 4-(N-nitroso)-acetamide AF4: in a three-necked round 50ml bottle were charged with AF4 acetamide (0.12 g, 0.25mmol), 10 ml n-butyl

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88 ether and 1-octene (47l, 0.30mmol). This mixture was heated to 110 and the p-chlorobenzoyl nitrite (0.12 g, 0.63mmol) in butyl ether (3ml) was added during 30 minutes with stirring. This mixture was maintained at this temperature over night and then was cooled. Solvent was evaporated under vacuum, and the residue was purified by silica gel chromatography. Reduced AF4 was separated (26mg, 32%) first, and then, t-butoxide ion adduct (45mg, 46%) was separated as a mixture with benzene adduct (1.7% from the 19 F NMR). 1 H NMR (300MHz, CDCl 3 /TMS) 7.66(d, J=8.1Hz, 1H), 7.12(m, 3H), 6.96(d, J=8.1Hz, 1H), 6.86(d, J=8.7Hz, 1H), 6.35(s, 1H), 1.23(s, 9H); 19 F NMR (282MHZ, CDCl 3 /CFCl 3 ) -110.52(d, J=243.1Hz, 1F), -114.08(d, J=236.0Hz, 1F), -114.88(d, J=235.8Hz, 1F), -115.05(d, J=235.8Hz, 1F), -116.07(d, J=236.9Hz, 1F), -117.1(d, J=238.0Hz, 1F), -118.09(d, J=238.3Hz, 1F), -119.08(d, J=237.2Hz, 1F). 4--acetamide AF4: 4-aminoAF4 (5 g, 13.6mmol) was dissolved in 100 ml acetic anhydride and the mixture was refluxed for 6 h. Then, reaction mixture was cooled to room temperature and solvent was evaporated under vacuum. The black residue was purified by silica gel column chromatography, then recrystallization from ethanol to give a white solid (5.12 g 92%), mp 183-185. 1 H NMR (300MHz, CDCl 3 /TMS) 8.38(s, 1H), 7.92(d, J=6.6Hz, 1H), 7.54(d, J=8.4Hz, 1H), 7.42(m, 2H), 7.32(d, J=8.4Hz, 1H), 7.2(d, J=8.4Hz, 1H), 7.11(d, J=8.4Hz, 1H), 2.55(s, 3H); 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -107.83(dq, J=249.8, 9.0Hz, 1F), -112.85(dd, J=240.8, 9.0Hz, 1F), -114.18(d, J=250.1Hz, 1F), -114.71(d, J=241.1Hz, 1F), -117.13(d, J=237.7Hz, 1F), -117.18(d, J=237.7Hz, 1F), -118.46(d, J=240.8Hz, 1F), -118.51(d, J=234.6Hz, 1F). p-Chlorobenzoyl nitrite: following the literature method, 102 to a sodium bicarbonate solution (9.0g, 0.11mol) in water was added 4-chlorobenzoic acid (17 g, 0.12

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89 mol). The solution was filtered hot and to the filtrate silver nitrate (19g, 0.11mol) in water was added during stirring. The precipitate silver p-chlorobenzoate was filtered and washed with ethanol (twice) and dried over P 2 O 5 under vacuum for one day. To a stirred suspension of silver p-chlorobenzoate (20 g, 75 mmol) in 180ml dry CCl 4 at -10 was added nitrosonium chloride (8g, 125mmol) during 30 minutes. The mixture was stirred for a further 20 minutes at -10and 1 h at room temperature. The mixture was filtered rapidly after that and residue was washed with CCl 4 twice. The filtrates were combined and evaporated under vacuum. The residue was distilled under vacuum (84-85/2.5mmHg) to give 12.1 g yellow-reddish solid (86%). Product was made into 0.86M solution in benzene or butyl ether for future use. 1-octene reacts with 4-(N-niroso)-acetamide AF4: a three-necked round 50 ml bottle was charged with AF4 acetamide (0.24 g, 0.5mmol), 10 ml n-butyl ether and 1-octene (80l, 1.0mmol). This mixture was heated to 110 and the p-chlorobenzoyl nitrite (0.16 g, 0.85mmol) in butyl ether was added during 30 minutes. This reaction mixture was maintained at this temperature over night. Then the mixture was cooled and solvent was evaporated under vacuum. The residue was purified on a silicon gel column and eluted with hexanes/ethyl acetate (100:1) to give oily product 1 (83%). 1 H NMR (300MHz, CDCl 3 /TMS) 7.33(m, 1H), 7.2(m, 2H), 7.1 (m, 2H), 7.0(d, J=8.1Hz, 1H), 6.86(s, 1H), 5.51(m, 1H), 5.33(m, 1H), 3.55(m, 1H), 3.3(m, 1H), 2.05(m, 2H), 1.3(m, 6H), 0.9(m, 3H); 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -110.7(d, J=242.5Hz), -111.2(d, J=244.2Hz), -113.6 (d, J=243.9Hz), -114.8 (d, J=241.1Hz), -115.8(d, J=237.7Hz), -117.5 (d, J=237.7Hz), -118.8 (d, J=238.0), -119.0 (d, J=240.8Hz); 13 C NMR (75MHz, CDCl 3 ) 142.5, 135.3, 134.7, 134.5, 133.3, 131.7, 130.4, 129.6, 129.3, 127.0, 126.5, 126.2, 125.2,

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90 123.5, 122.5, 119.6, 119.0, 115.5, 36.8, 32.7, 31.6, 29.4, 22.7, 14.3; MS(EI) m/z 462(M + )(15), 391(16), 365(17), 189(45), 215(19), 176(100), HRMS Calc. for C 24 H 22 F 8 462.1594, Found 462.1593 (EI); Elemental analysis Calc. for C 24 H 22 F 8 : C: 62.34, H: 4.795; Found C: 62.42, H: 5.01. IAF4 with 1-Octene: the procedure was the same as AF4-yne DA reactions under Cram conditions if butyl ether was the solvent. There was no other product except the reduced AF4, and there was no trace amount of ene reaction product from crude 19 F NMR. The reaction was refluxed at 123 for 30 minutes if 1-octene was the solvent, which gave the same result as above. Anthracene, naphthalene and benzene with 4-(N-nitroso)-acetamide AF4: the reaction of naphthalene was carried out in butyl ether (10ml) at 110 while anthracene and benzene were reacted in refluxing benzene (10ml). Yields checked with ,,-trifluoromethylbenzene as standard were of 95%, 93% and 90% respectively. The isomer ratio of anthracene adduct varied from 97:3 to 95:5, while that of naphthalene adduct changed from 8-10% exo-adduct to 15-17% exo-adduct. Norbornadiene with 4-(N-nitroso)-acetamide AF4: the reaction procedure was the same as above except that norbornadiene (54mg, 63l, 0.59mmol, 2equiv) was the substrate. Products were a mixture of four compounds with the ratio of [2+2+2]-endo: [2+2+2]-exo: [2+2]-endo:[2+2]-exo/39:21:21:19 in a combined yield of 67%. Cyclopentene with 4-(N-nitroso)-acetamide AF4: the procedure was the same as above except that n-butyl ether was the solvent and cyclopentene (2 equivalents, 0.22ml) was the reactant. The yield was 53% with two stereoisomers 2a and 2b ratio of 5.6:1. 1 H NMR (500MHz, CDCl 3 /TMS) Isomer1 7.16(d, J=8.5Hz, 2H), 7.08(d, J=8.5Hz, 2H),

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91 7.02(s, 1H), 6.92(s, 1H), 6.88(d, J=8.5Hz, 1H), 5.65 (m, 1H), 5.23(m, 1H), 4.23(m, 1H), 2.52(m, 3H), 2.15(m, 1H); 13 C NMR(126MHz, CDCl 3 ) 146.5, 135.4, 135.4, 135.4, 135.0, 135.0, 131.1, 130.3, 130.3, 129.4, 129.4, 129.4,127.3, 127.8, 118.9, 118.9, 119.8, 118.9, 47.0, 32.9, 30.3; Isomer2 7.17(m, 1H), 7.16(m,1H), 7.08(m, 2H), 7.04(m, 1H), 6.88(m, 1H), 6.83(s, 1H), 6.07(m, 1H), 5.86(m, 1H), 4.15(m, 1H), 2.24(m, 3H), 1.15(m, 1H); 13 C NMR (75MHz, CDCl 3 ) 148.1, 136.1, 135.4, 135.4, 135.4, 135.0, 130.3, 130.3, 130.3, 129.4, 129.4, 129.4, 127.3, 127.8, 118.9, 118.9, 119.8, 118.9, 47.8, 34.8, 31.9; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) isomer1 -109.9, -112.7(AB, J=241Hz), Iosmer2 -107.9, -112.9(AB, J=244Hz); MS(EI) m/z 418(M + )(33), 242(100), 176(28); HRMS Calc. for C 21 H 14 F 8 418.0967, Found 418.0942 (EI); Elemental analysis Calc. for C 21 H 14 F 8 : C: 60.29, H: 3.37; Found: C:60.08, H: 3.38. Cyclohexene with 4-(N-nitroso)-acetamide AF4: to a mixture of AF4 acetamide (0.30g, 0.73mmol), and cyclohexene (0.15ml, 1.5mmol) in 20 ml butyl ether was added p-chlorobenzonitrite butyl ether solution (4.8ml 0.3M) slowly at 110. This mixture was stirred overnight at this temperature. Solvent was evaporated under vacuum and the residue was purified through silica gel chromatography. White solid 0.175 g was obtained in 55% yield, which was analyzed as a mixture of ennationmers (3a and 3b) in 1:1 ratio. 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -109.08(d, J=243.93Hz), 109.82(d, J=243.93Hz), -111.72(d, J=243.93Hz), -112.85(d, J=243.93Hz), -115.28(d, J=241.11Hz), -116.57(d, J=241.11Hz), -116.86(d, J=240.83Hz), -117.13(d, J=237.73Hz), -117.47(d, J=240.83Hz), -117.58(d, J=240.83Hz), -119.0(d, J=238.01Hz), -119.25(d, J=237.73Hz), -119.33(d, J=240.83Hz), -119.54(d, J=240.83Hz); Isomer 1 1 HNMR (500MHz, CDCl 3 /TMS) 1.10, 1.82(m, 2H), 1.21, 1.43(m, 2H), 1.94(m, 2H), 3.71(m, 1H), 5.82(dq, J=10.4, 2.5Hz, 1H),

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92 6.07(dtd, J=10.1, 3.7, 2.1Hz, 1H), 6.93(s, 1H), 6.96(s, 1H), 7.03(s, 1H), 7.04(s, 1H), 7.12(s, 3H); 13 C NMR (126MHz, CDCl 3 ) 19.9, 25.2, 33.7, 38.1, 119.0, 119.0, 119.0, 120.0, 126.7, 127.6, 129.4, 129.4, 129.4, 129.4, 129.4, 132.1, 135.4, 135.4, 132.6, 134.6, 134.6, 148.1, Isomer 2 1 HNMR (500MHz, CDCl 3 /TMS) 1.75, 1.94(m, 2H), 1.84, 2.18(m, 2H), 1.98, 2.01(m, 2H), 3.71(m, 1H), 5.09(dq, J=9.9, 2.0Hz, 1H), 5.53(dq, J=10.0, 3.3Hz, 1H), 6.90(s, 1H), 6.98(s, 1H), 7.00(s, 1H), 7.06(s, 1H), 7.09(s, 2H), 7.16(s, 1H); 13 C NMR (126MHz, CDCl 3 ) 22.2, 24.7, 27.6, 38.6, 119.0, 119.0, 119.0, 120.0, 127.6, 127.6, 129.4, 129.4, 129.4, 129.4, 129.4, 131.6, 132.6, 134.6, 134.6, 135.4, 135.4, 146.4; MS (EI) m/z 432(M + )(33), 255(100), 176(78); HRMS Calc for C22H16F8 432.1124, Found 432.1104 (EI). -Methylstyrene with 4-(N-nitroso)-acetamide AF4: to a mixture of AF4 acetamide (0.30g, 0.73mmol), and -methylstyrene (0.48ml, 3.6mmol) in 20 ml butyl ether was added p-chlorobenzonitrite butyl ether solution (4.8ml 0.3M) slowly at 110. This mixture was stirred overnight at this temperature. Solvent was evaporated under vacuum and the residue was purified through silica gel chromatography. White solid 0.252 g was obtained in 65% yield, which includes three products, ene reaction product (4) 37%, Diels-Alder product (5)24% and hydrolyzed ene product (6) 4%. Ene product 4: 1 HNMR (500MHz, CDCl 3 /TMS) 3.54(dd, J=17.0, 2.6Hz, 1H), 4.08(d, J=16.6Hz, 1H), 4.67(q, J=1.3Hz, 1H), 5.35(q, J=0.8Hz, 1H), 6.87(d, J=8.6Hz, 1H), 6.91(d, J=8.6Hz, 1H), 7.02(d, J=8.8Hz, 1H), 7.09(d, J=9.2Hz, 1H), 7.13(d, J=8.8Hz, 1H), 7.22-7.32(m, 7H); 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -111.76(d, J=243.93Hz, 1F), -113.67(d, J=243.93Hz, 1F), -114.99(d, J=240.83Hz, 1F), -115.94(d, J=240.83Hz, 1F), -117.63(d, J=237.73Hz, 1F), -117.68(d, J=237.73Hz, 1F), -119.23(d, J=241.11Hz, 1F),

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93 119.38(d, J=240.83Hz, 1F); 13 C NMR (126MHz, CDCl 3 ) 145.9, 140.7, 140.6, 135.4,134.6, 130.2, 134.8, 132.1, 132.7, 132.1, 130.4, 129.6, 129.4, 128.1, 128.1,127.5, 126.3, 126.5, 126.3, 119.7, 118.8, 118.9, 118.8, 116.2, 39.0; MS (EI) m/z 468(M + )(35), 292(16), 291(57), 241(100), 176(58); HRMS Calc for C 25 H 16 F 8 468.1124, Found 468.1115 (EI). Diels-Alder product 5: 1 HNMR (500MHz, CDCl 3 /TMS) 2.77(s, 3H), 6.13(d, J=8.6Hz, 1H), 6.47(dq, J=8.7, 1.8Hz, 1H), 7.23-7.24(m, 2H), 7.34(dq, J=8.4, 1.7Hz, 1H), 7.39(d, J=8.4Hz, 1H), 7.55(t, J=7.6Hz, 1H), 7.64(ddd, J=8.3, 7.4, 1.4Hz, 1H), 7.78(d, J=3.3Hz, 1H), 7.99(d, J=8.3Hz, 1H), 8.17(t, J=8.7Hz, 1H); 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -103.5(d, J=253.24Hz, 1F), -215.56(d, J=251.54Hz, 1F), -111.38(dt, J=247.03, 12.13Hz, 1F), -112.93(d, J=247.03Hz, 1F), -113.59(d, J=240.83Hz, 1F), -117.14(dd, J=238.01, 12.13Hz, 1F), -118.86(dd, J=237.73, 6.2Hz, 1F), -121.44(d, J=240.83Hz, 1F); 13 C NMR (126MHz, CDCl 3 ) 136.2, 134.3,133.6, 133.1, 132.1, 131.8, 130.0, 129.8, 129.9, 129.9, 129.8,129.8, 128.8,128.3, 127.8, 127.2, 127.1, 120.5, 123.5, 125.9, 119.7, 118.8, 118.8, 118.1, 20.5; MS (EI) m/z 466(M + )(77), 291(12), 290(66), 289(100), 275(93), 176(28); HRMS Calc for C25H14F8 466.0968 Found 466.0959; UV (CH 2 Cl 2 ): max (log ) = 395.0 (3.27), 379.0 (3.20), 318.3(3.79), 292.0(4.31). Hydroxyl product 6: 1 HNMR (500MHz, CDCl 3 /TMS) 1.84(s, 3H), 2.55(d, J=17.5Hz, 1H), 3.41(dd, J=18.1, 4.6Hz, 1H), 6.82(d, J=8.7Hz, 1H), 6.85(d, J=8.5Hz, 1H), 6.97(d, J=8.6Hz, 1H), 7.25(d, J=8.8Hz, 1H), 7.27(m, 1H), 7.32(m, 2H), 7.35(d, J=8.0Hz, 1H), 7.43(d, J=8.6Hz, 1H), 7.49(m, 2H), 7.71(d, J=8.4Hz, 1H); 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -106.49(dd, J=247.03, 9.3Hz, 1F), --110.48(d, J=259.16Hz, 1F), -110.51(d, J=243.93Hz, 1F), -110.65(d, J=249.85Hz, 1F), -112.69(dd, J=241.11, 9.02Hz,

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94 1F), -115.66(d, J=237.73Hz, 1F), -119.46(d, J=238.01Hz, 1F), -121.64(d, J=240.83Hz, 1F); 13 C NMR (126MHz, CDCl 3 ) 138.5, 135.6, 134.6,134.8, 134.4,133.6, 131.2,131.1, 131.7, 130.7, 130.5, 130.4, 128.9, 128.4, 128.4, 127.0, 122.8, 122.8, 120.0,119.8, 118.9, 118.7, 68.2, 38.3, 27.9; MS (EI) m/z HRMS Calc for C25H18F8O 486.1230, Tetracyclone with 4-(N-nitroso)-acetamide AF4: to a n-butyl ether solution of 1,1,2,2,9,9,10,10-octafluoroparacyclophane 4-acetamide (0.32g, 0.78mmol) and 2,3,4,5-tetraphenylcyclopentadiene (0.33g, 0.85mmol) in a three necked round bottom flask was added p-chlorobenzoyl nitrite (2.5 ml, 0.47M) in n-butyl ether in 10 minute at 110. The mixture was stirred at this temperature overnight. The solvent was eveaperated under vacuum, and product was separated by silica gel chromatography using the hexane:dichloromethane (10:1) as eluent. The yield was 83% with internal methyl benzoate standard. 1 HNMR (500MHz, CDCl 3 /TMS) 7.45(s, 2H), 7.35(d, J=8.0Hz, 2H), 7.30(s, 2H), 7.15(t, J=7.7Hz, 4H), 7.09(t, J=7.4Hz, 2H), 7.07(s, 2H), 6.95(t, J=7.0Hz, 2H), 6.93(s, 2H), 6.89(t, J=7.5Hz, 2H), 6.80(d, J=7.2Hz, 2H), 6.64(t, J=7.6Hz, 2H), 6.03(d, J=7.7Hz, 2H); 13 C NMR (126MHz, CDCl 3 ) 143.5, 142.6, 139.7, 138.6, 138.6, 133.5, 132.9, 132.4, 131.7, 132.3, 131.1, 129.9, 128.0, 127.4, 127.1, 127.1, 126.6, 126.4, 126.5, 125.9, 117.8, 117.7; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -107.73 (d, J=252.95Hz, 2F), -109.86(d, J=250.13Hz, 2F), -116.25(d, J=240.83Hz, 2F), -120.80(d, J=240.83Hz, 2F); MS (EI) m/z 706(M + )(14), 526(26), 352(6), 176(100); HRMS Calc for C44H26F8, 706.1907; Found 706.1933 (EI). Cycloheptatriene with 4-(N-nitroso)-acetamide AF4: the procedure was the same as above except that cycloheptatriene (81mg, 91l, 0.88mmol, 2equiv) was used as the substrate. The mixture was worked up by usual way and two products were obtained.

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95 8a: 1 HNMR (500MHz, CDCl 3 /TMS) 7.40(s, 1H), 7.36(s, 2H), 7.19(s, 1H), 7.13(s, 1H), 7.08(s, 1H), 7.06(s, 1H), 6.95(s, 1H), 6.94(d, J=7.6Hz, 1H), 6.89(s, 1H), 6.70(d, J=8.4Hz, 1H), 6.67(d, J=9.3Hz, 1H), 6.53(s, 1H), 6.23(t, J=7.1Hz, 1H), 6.17(t, J=6.9Hz, 1H), 4.89(t, J=5.4Hz, 1H), 4.74(s, 1H), 2.54(s, 1H), 1.97(dt, J=8.6, 4.3Hz, 1H), 1.67(dt, J=8.0, 4.0Hz, 1H); 13 C NMR (126MHz, CDCl 3 ) 143.9, 143.6, 141.4, 134.2, 133.9, 133.1, 133.1, 132.8, 132.5, 132.1, 131.4, 130.8, 129.2, 128.6, 128.6, 128.5, 128.3, 127.6, 127.6, 127.3, 126.8, 126.6, 126.5, 126.5, 125.4, 125.2, 118.6, 118.6, 118.2, 117.4, 117.4, 117.4, 117.6, 117.4, 37.4, 37.1, 27.1, 26.4, 24.4; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) 8b: 1 HNMR (500MHz, CDCl 3 /TMS) 7.31(d, J=8.8Hz, 1H), 7.19(s, 1H), 7.17(s, 1H), 7.10(s, 1H), 7.04(s, 1H), 7.01(s, 1H), 6.94(d, J=7.6Hz, 1H), 6.85(d, J=8.9Hz, 1H), 6.84(d, J=9.3Hz, 1H), 6.84(s, 1H), 6.82(s, 1H), 6.81(s, 1H), 6.55(t, J=7.1Hz, 1H), 6.49(td, J=6.8, 1.5Hz, 1H), 6.11(s, 1H), 4.94(t, J=5.0Hz, 1H), 4.74(m, 1H), 2.45(s, 1H), 1.30(dt, J=8.7, 4.2Hz, 1H), 0.94(dt, J=8.3, 4.2Hz, 1H); 13 C NMR (126MHz, CDCl 3 ) 143.9, 144.1, 140.9, 133.9, 133.9, 133.1, 133.1, 131.0, 132.8, 130.9, 129.0, 129.2, 129.1, 128.5, 128.4, 128.3, 128.3, 127.6, 126.9, 126.1, 125.8, 125.5, 125.4, 125.0, 125.0, 118.9, 118.6, 118.2, 117.4, 117.7, 117.6, 117.6, 117.6, 36.9, 36.6, 26.4, 24.4, 25.0; MS (EI) m/z 792(M + )(14), 442(2), 352(8), 177(19), 176(100); HRMS (EI), Calc for C 39 H 20 F 16 792.1309, found 792.1331. 9a: 1 HNMR (500MHz, CDCl 3 /TMS) 7.18(s, 1H), 7.16(d, J=8.8Hz, 2H), 7.04(d, J=8.4Hz, 1H), 6.99(d, J=7.8Hz, 1H), 6.70(dd, J=10.6, 5.7Hz, 1H), 6.62(dd, J=10.6, 5.9Hz, 1H), 6.45(dd, J=9.5, 6.1Hz, 1H), 6.04(dd, J=9.2, 6.1Hz, 1H), 5.50(dd, J=9.3, 5.8Hz, 1H), 4.58(dd, J=8.6, 6.2Hz, 1H), 3.06(t, J=5.9Hz, 1H); 13 C NMR (126MHz, CDCl 3 ) 142.9, 130.9, 134.0, 133.3, 131.2, 130.0, 129.4, 128.2, 128.2, 127.5, 126.7, 126.7, 126.8, 126.8,

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96 125.5, 123.2, 120.2, 118.4, 117.9, 117.6, 117.6, 116.2, 39.1; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -110.75(d, J=225.0Hz, 1F), -111.62(d, J=224.8Hz, 1F), -111.80(d, J=229.5Hz, 1H). -111.91(d, J=244.2Hz, 1F), -112.18(d, J=244.2Hz, 1F), -112.66(d, J=229.8Hz, 1F), -114.31(d, J=244.5Hz, 1F), -114.39(d, J=239.4Hz, 1F), -115.0(d, J=244.2Hz, 1F), -115.91(d, J=95.6Hz, 1F), -116.0(d, J=112.5Hz, 1F), -115.99(d, J=177.7Hz, 1F), 9b: 1 HNMR (500MHz, CDCl 3 /TMS) 7.27(d, J=9.8Hz, 1H), 7.11(d, J=9.8Hz, 2H), 7.09(s, 2H), 6.98(s, 2H), 6.53(d, J=5.8Hz, 1H), 6.26(dd, J=9.0, 2.2Hz, 1H), 6.24(s, 1H), 5.49(m, 1H), 5.47(m, 1H), 2.42(m, 1H), 2.37(m, 1H); 13 C NMR (126MHz, CDCl 3 ) 142.6, 139.3, 133.4, 134.0, 133.3, 131.2, 130.9, 128.2, 128.2, 127.5, 126.9,126.7, 126.7,126.8, 126.8, 125.0, 122.1, 120.1, 117.6, 117.9, 117.6, 118.4, 26.6. MS (EI) m/z 442(M + )(29), 352(9), 265(70), 177(17), 176(100); HRMS Calc for C 23 H 14 F 8 442.0968, found 442.0977. 1,1-Dideuterobutanol: Following the published procedure, 135 to lithium aluminum deuteride (15g, 0.357mol) solution in ethyl ether (300ml) in a one-liter three-necked flask equipped with refluxing condenser, dropping funnel and magnetic stirrer, and protected nitrogen flow, was added dropwise a ethyl ether (150ml) solution of butyric acid (27.5 ml, 0.30mol) at a rate such as to produce gentle reflux. Thirty minutes after the addition has been completed and with continued stirring and cooling of the flask, water was added cautiously to decompose excess hydride. Then 150 ml of 10% H 2 SO 4 was added (the flask may have to be cooled in ice water) and a clear solution results. The product was separated from the water solution and the water solution was extracted with 100 ml ethyl ether three times. Organic layers were combined together and purified by fractional

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97 distillation through a 24 inch column to give 21.4 g clear liquid (115-116). 1 HNMR (300MHz, CDCl 3 /TMS) 2.72(s, 1H), 1.49(t, J=7.8Hz, 2H), 1.34(m, 2H), 0.88(t, J=7.2Hz, 3H). 1,1-Dideuterobutyl bromide: As in the literature procedure, 136 to a solution of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) (39.68g, 0.175mol) in dry methylene chloride (200ml) was added triphenylphophine (45.86g, 0.175mol) cautiously, then tetrabutyl ammonium bromide (56.35g, 0.175mol), at room temperature. 1,1-dideuterobutanol (11.07g, 0.145mol) was then added to the mixture. The yellow color of the mixture immediately changed to deep red. The liquid phase was vacuumed out by pump and fresh methylene chloride 100 ml was added to the mixture to extract product twice. The liquid phase was combined together and fractional distilled to give 7.5 g product (38%) (80-90). 1 HNMR (300MHz, CDCl 3 /TMS) 1.82(t, J=7.5Hz, 2H), 1.46(m, 2H), 0.92(t, J=7.5Hz, 3H). 1,1,1,1-Tetradeuterobutyl ether: to a suspension of sodium hydride (4.7g, 60%, 0.118mol) in tetrahydrofuran (THF) (50ml) was added slowly 1,1-dideuterobutanol (4.09g, 54mmol) in 10ml THF at room temperature. The mixture was heated to reflux and kept refluxing for 20 h. Then, the mixture was cooled to room temperature, 1,1-dideuterobutyl bromide (7.5g, 54mmol) in 10 ml THF was added slowly to the mixture. The reaction mixture was kept refluxing for 23 h and then cooled to room temperature again. Water (20 ml) was added slowly to the mixture to destroy excess sodium hydride. After that, 100ml water was added and mixture was extracted with ethyl ether (50ml) four times. Organic phase was combined together and distilled through a 24 inch column to collect from 80-120 then redistill to give 6.3 g product (115-116, 66%). 1 HNMR

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98 (300MHz, CDCl 3 /TMS) 1.53(t, J=6.9Hz, 4H), 1.35(m, 4H), 0.92(t, J=6.0Hz, 3H); 13 C NMR (75MHz, CDCl 3 ) 69.96(m), 31.84, 19.51, 14.16; MS (EI) m/z 134(M + )(12), 91(100), 76(35), 74(35), 60(83); HRMS Calc for C 8 H 14 D 4 O 134.1608, Found 134.1603. Reaction of IAF4 with KO t Bu in 1,1,1,1-tetradeuterobutyl ether: to a IAF4 (60mg, 0.12mmol) in 2ml 1,1,1,1-tetradeuterobutyl ether solution was added KO t Bu (70mg, 0.62mmol) and refluxed for 20 h. The reaction mixture was worked up by the usual method and products were purified by preparative TLC plates. First product was the ether adduct plus reduced AF4 and second one was IAF with reduced AF4. Reaction of IAF4 with KO t Bu/DO t Bu: to a IAF4 (0.16g, 0.33mmol) in 10 ml butyl ether solution was added KO t Bu (0.18g, 1.65mmol) and DO t Bu (0.16ml, 1.65mmol). The mixture was kept for refluxing for 5 h and worked up as usual way. AF4 was separated by silica gel chromatography and then preparative TLC. AF4 (35mg, 30%) was obtained along with ether adducts. MS (EI) m/z: 353 (7), 352(6), 177(28), 177(10), 176(100). Reaction of IAF4 with KO t Bu/CD 3 CN: to a IAF4 (0.12g, 0.25mmol) solution in CD 3 CN (4ml) was added KO t Bu (0.17g, 1.5mmol). The mixture turned black immediately and was kept refluxing for half hour. The mixture was cooled and worked up by the usual way. Products were separated by silica gel chromatography. AF4 (46mg, 52%) was obtained along with ring opening product (8mg, 8%). MS (EI) m/z: 354(19), 353(31), 353(12), 352(9), 178(54), 177(54), 177(35), 176(100).

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CHAPTER 4 EFFICIENT SYNTHESES OF NOVEL NAPHTHALENOAND ANTHRACENO-OCTAFLUORO[2.2]PARACYCLOPHANES 4.1 Introduction Since the isolation of the parent compound by Brown et al. in 1949 2 and its first directed synthesis by Cram et al. in 1951, 14 interest in molecules containing the unique structural features of [2.2]paracyclophanes has never waned and has generated a literature filled with unusual structural features and chemistry. 31 The characteristic proximity of the face-to-face aromatic rings, coupled with the rigid skeleton and high strain energy of the [2.2]paracyclophane system, leads to unique transannular interactions that affect both the chemistry and the spectroscopy of these systems. 100, 137 One of most interesting aspects of the chemistry of [2.2]paracyclophanes is their ability to be cracked thermally, via a 1,6-cleavage process, forming a highly reactive p -xylylene species. This characteristic serves as the basis for the important commercial application of [2.2]paracyclophanes as precursors of parylene-type polymers formed via a vapor deposition process. 138 Anthracenophane (1) and naphthalenophane (2) (Figure 4-1) are synthesized by Toyada 29, 30 and Wasserman 9, 21, 25 respectively. The yields are poor, with 41% as the best yield. Both synforms of anthracenophane and naphthalenophane are converted to antiforms by heating above 240. 99

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100 anti-1syn-1anti-2syn-2 Figure 4-1 Anthracenophane 1 and naphthalenophane 2 [2.2](1,4)(9,10)Anthracenophane (3), as well as [2, 2] paracyclo(9,10) anthracenophane (4) and [2,2] (1,4)naphthaleno(9,10)anthracenophane (5) (Figure 4-2), are synthesized from a cross hofmann elimination of quaternary ammonium hydroxides. 139 They show significant transannular -electron interaction compared to their open chain analogues. 345 Figure 4-2 [2.2](1,4)(9,10)anthracenophane 3, [2.2] paracyclo(9,10) anthracenophane 4 and [2.2](1,4)naphthaleno(9,10)anthracenophane 5 While non-fluorinated cyclophanes have been synthesized and studied, 12 the fluorinated ones are scarce. Tetrafluoro [2,2] paracyclophane (6) has only 1% yield via the Wurtz coupling reaction. 31 Polyfluoroaryl [2,2] cyclophanes (6) and (7) (Figure 4-3)

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101 are synthesized by Filler et al. 140, 141 Compound (6) shows transanunular donor-acceptor interaction, where the tetrafluorophenylene acts as an electron withdrawing -acid. 142 This effect makes compound 6 inert to electrophilic attack. F F F F F F F F F F F F 67 Figure 4-3 Polyfluoroaryl [2.2]cyclophanes 6 and 7 The totally bridge fluorinated [2.2]paracyclophane, 1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane (AF4, Figure [ 1 -3]), has only become accessible during the last decade since the relatively simple syntheses of Dolbier were published. 43-45 The presence of the bridge fluorines makes AF4 the thermal precursor of an extremely thermally stable parylene polymer with numerous novel properties, and their presence also bestows novel chemical behavior to the [2.2]paracyclophane itself. 48 As such, AF4 is highly deactivated towards electrophilic aromatic substitution, although synthetic procedures have been developed to allow the preparation of virtually any monoor multi-substituted derivative desired. 51, 52 Recently it has been shown that the iodo derivatives, monoor bis-, serve as unexpectedly efficient precursors of aryne or bis-aryne derivatives of AF4 which undergo high yield Diels-Alder reactions with benzene, naphthalene, and other aromatics (Figure 4-4). 50

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102 F F F F F F F F F F F F F F F F F F F F F F F F KOtBu, Butyl ether refluxI 89 F F F F F F F F F F F F F F F F F F F F F F F F KOtBu, Butyl ether refluxI 1011I Figure 4-4 Diles-Alder reaction of mono and bis-AF4-yne Looking at the Diels-Alder (DA) products of mono and bis-AF4-yne, bridge fluorinated [2.2]cyclophane may be generated by getting rid of one or two molecules of ethylene from the adducts. In this chapter we will show how the monoand bis-adducts with benzene and naphthalene, 8-11 (Figure 4-4), can be used to prepare the four novel

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103 naphthaleno and anthraceno derivatives of AF4 12-15 (Figure 4-5), respectively, in an efficient, one-pot process. F2C CF2 F2C CF2 F2C CF2 F2C CF2 F2C CF2 F2C CF2 F2C CF2 F2C CF2 12131415 Figure 4-5 Bridge fluorinated [2.2]cyclophane 12, 13, 14 and 15 4.2 Results and Discussion [2.2]Paracyclophanes containing condensed polycyclic aromatic subunits have been prepared with one or two naphthalenes 9, 21, 25, 143-146 and anthracenes, 29, 139, 147 and their novel structural topology gives rise to unusual spectroscopic properties that clearly derive from their characteristic face to face aromatic systems. 21, 137, 148, 149 The syntheses of these compounds were generally via multi-step processes that resulted in overall low yields. In contrast, the analogous bridge fluorinated, AF4-derived naphthalenoand anthraceno-[2.2]phanes can be readily synthesized via one-pot procedures involving the reaction of 3,6-dipyridinyl-1,2,4,5-tetrazine ( 16 ) with the monoand bis-Diels-Alder adducts 8-11 As exemplified in the reaction of adduct 8 with 16 (Figure 4-6), the conversion to 12 involves a three-step process beginning with a DA reaction of 8 with 16 to form the presumed intermediate adduct 17 This adduct then loses N 2 to form

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104 intermediate 18 which undergoes a rapid double aromatizing retro-Diels-Alder reaction to form the bridge fluorinated [2.2](1,4)naphthalenoparacyclophane, 12 (mononaphthophane) in an isolated yield of 89%. F F F F F F F F NNNN Pyr Pyr F F F F F F F F Pyr N Pyr NN N H H N N Pyr Pyr H H NN Pyr Pyr pentyl etherreflux, 187oCN2 fast816171812 +Figure 4-6 Reaction of adduct with 3,6-dipyridinyl-1,2,4,5-tetrazine 16 Likewise, the [2.2](1,4)anthracenoparacyclophane, 13 (mono-anthophane) the anti -[2.2](1,4)napth-alenophane, 14 (bis-naphthophane) and the anti -[2.2](1,4) anthracenophane, 15 (bis-anthophane) were obtained in 87%, 85% and 85% yields, respectively. All were fully characterized by 1 H, 13 C, and 19 F NMR spectroscopy, and by mass spectrometry. The mass spectra was characterized by small signals due to parent ions (of exact mass consistent with structure) and large signals of ions derived from the respective p -xylylenes obtained from the expected 1,6-fragmentation of the parent species. Thus the base peak in the (EI) mass spectrum of 12 was at mass 226 and derived from the p -xylylene 19 radical cation (Figure 4-7 ). A 47% signal at mass 176 was derived from the

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105 other p -xylylene fragment 20 (Figure 4-7]), whereas the signal for the parent ion at mass 402 was present only in the relative amount of 24%. Mass spectra of the other three products were also consistent with expectations based on predominant 1,6-fragmentation in the mass spectrometer. CF2 CF2 CF2 CF2 M+ 226 (100)M+ 176 (47)1920 Figure 4-7 Fragment of [2.2]cyclophane 12 The chemical shifts of the 13 C and 1 H NMR spectra of products 12 15 are given pictorially in Figure 4-8. In general they show the same trends as were observed in the hydrocarbon series, although the presence of the bridge fluorines cause virtually all of the protons to appear at lower fields than their counterparts in the hydrocarbon series. Complete 1 H and 13 C chemical shift assignments for compounds 12 14 were made based on the one bond and long range 1 H13 C couplings, seen in their GHMBC spectra. In the anthracene moiety, the peri of the two protons that display an A2B2 pattern couples with a protonated carbon on the other ring. For the naphthalene moiety, this proton couples with the carbon ipso to the CF 2 group, which is a triplet. Couplings to this carbon, and to the CF 2 carbon that is a triplet of triplets identifies the proton of the naphthalene (anthracene) moiety that is ortho to the CF 2 group. Similar couplings were observed for the para -phenylene moiety in mono-naphthophane 12 and mono-anthophane 13 The shielded one of the two protons on this moiety displayed a nOe with the proton peri to the CF 2 group on the naphthalene (anthracene) moiety. In all of the compounds, this latter

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106 proton also displayed a ca 2-3 Hz coupling with one of the fluorines, presumably a through-space coupling with the closest fluorine. F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F 12131415AF47.16129.86.84129.3133.46.24122.77.45127.8132.1131.7118.7119.9125.48.08128.97.61133.36.90128.85.90123.2118.7120.07.37127.7129.2131.4124.78.63128.98.03128.07.61132.36.41124.5129.5119.5131.6124.98.13128.37.606.078.738.077.60 Figure 4-8 Chemical shifts of [2.2]cyclophane 12, 13, 14 and 15 The proton on naphthalene and ortho to the CF2 group is more shielded in bis-naphthophane 14 than in mono-naphthophane 12 (6.41 vs. 7.45); therefore the orientation of the two naphthalene groups in bis-naphthophane 14 is anti. On the basis of similar facts, it was concluded that bis-anthophane 15 is also anti.

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107 Bis-anthophane 15 had poor solubility in all of the deuterated solvents that we tried. Even in tetrachloroethane-d2, at 70 C, a 24 hours GHMBC spectrum did not afford any cross-peaks. The assignments of the proton chemical shifts for bis-anthophane 15 were based on the chemical shift trends that were common to the other three compounds. Mono-anthophane 13 was not stable in solution; dimer 16 was formed in 33% yield when an NMR sample was allowed to stand for one week in deuterated chloroform solution at room temperature. This dimer was also observed in the reaction crude mixture (10%) when mono-anthophane 13 was synthesized. However, trying to dimerize the pure monomer under varied conditions proved difficult even under reflux conditions in pentyl ether, which was the condition where dimer was observed in the synthesis of mono-anthophane 13. Subjecting the chloroform solution of monomer, mono-anthophane 13, to sunlight led to a complicated reaction mixture, which included the dimer. Interestingly, dimerization could be cleanly observed when a sample of the chloroform solution of mono-anthophane 13 was subjected to fluorescent light. A 32% yield of dimer was obtained after one week at room temperature. Dimer was also seen to decompose to monomer under different wavelength light conditions. When the dimer solution in CDCl 3 was irradiated with UV light (>356nm) at room temperature in an NMR tube, monomer was detected in 86% yield by proton NMR after 15 h. The dimer structure was confirmed by both NMR analysis and crystalline x-ray diffraction analysis (Figure 4-10 and Appendix Figure 8).

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108 F F F F F F F F F F F F F F F F F F F F F F F F 6.36128.4116.8133.76.02126.1131.67.60128.47.40129.86.74132.47.55127.9131.27.40127.6129.87.33128.17.18131.9122.76.31128.8121.950.8118.04.2143.2128.55.70134.3118.1115.0 CDCl3room tempdimerize21 Figure 4-9 Dimerization of phenyl anthracenophane 21 Figure 4-10 ORTEP drawing of compound 21 The x-ray diffraction analysis indicates that there are two molecules of 21 in its asymmetric unit. Aromaticity in the anthracene moiety was broken and linked to each other by head to tail fashion; for molecule A, the center cyclobutyl ring had a twist angle of 31.8 o and a torsion angle C1-C2-C3-C4 of 22.4 o to relieve the steric strain of the two bulky anthracene moieties. The two fluorine bridges C1-C9-C10-C11 and C14-C17-C18-C7 had torsion angles 40.1 o and 26.9 o respectively, in molecule A. The anthracene moiety in bonds C5-C1-C2-C8 and C27-C3-C4-C30 had torsion angles 29.5 o and 33.2 o

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109 respectively.In molecule B, the cyclobutyl ring had a twist angle of 23.5 o with torsion angles of 35.1 o and 20.6 o in the two fluorine bridges. 4.3 UV and Fluorescence Spectrum The transannular interactions between systems with -electron distributions remain a subject of considerable interest. The majority of recent research has focused on the phenomenon termed formation of excimers. 150, 151 The criterion for implication of an excimer is the structureless fluorescence band which is red shifted from the normal fluorescence band. Figure 4-11 illustrates the UV absorption spectra of all 12-15 samples. They are unremarkable and closely resemble those of their hydrocarbon counterparts. 9, 21, 28, 139 All the bands of bis-naphthophane 14 and bis-anthophane 15 have red shifted from these of their non fluorinated counterparts, which are themselves all red shifted compared to the 1,4-dimethyl naphthalene and 1,4-dimethyl anthracene. In bis-naphthophane 14, the main band of the absorption spectrum shifted from 310 nm in a non fluorinated anti-[2.2]naphthalenoparacyclophane to 319 nm in a fluorinated one. Two new small bands emerged in the absorption spectrum of bis-anthophane 15 at 303 nm and 315 nm respectively. The main band in bis-anthophane 15 red shifted to 412 nm from 400 nm in the anthraceno[2.2]paracyclophane and extended beyond 450 nm. These red shifts in anthophane 13 and 15 are due to the extended electron conjugation and decreasing energy gap of their -* transitions compared to these of naphthophane 12 and 14. The emission spectra of all four compounds are given in Figure 4-12. The spectra are normalized to the same intensity to compare their band shift. Because of the solubility issue for bis-anthophane 15, all the spectra all are carried out in dichloromethane solution.

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110 Wavelength /nm 250300350400450500 2.02.53.03.54.04.55.05.5 12 13 14 15 log Figure 4-11 UV spectra of bridge fluorinated [2.2]cyclophanes 12 15 An excimer state has been shown to be the intermediate in the photodimerization reaction of anthracene, 152 in which an excited molecule is associated with a second molecule in the ground state. Ferguson et al. found that this excimer type emission could not be observed in the case of a stable anthracene dimer where only normal emission spectrum was observed, 153 which was supported by theoretical calculation. 154 In the study of excimer fluorescence of non-fluorinated anthracenophane, Hayashi et al. 155 found that no emission spectra due to the excimer states of [2.2](9,10)anthracenophane and anti-[2.2](1,4)anthracenophane could be observed at room temperature as well as at 77K. However, the excimer fluorescence was observed in syn-isomer of the latter one. 155 Similar result was obtained in synand antiisomer of

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111 [2.2](1,4)naphthalenophane, i.e., excimer emission was found in the syn-isomer but not in the anti-isomer. 156 All the emission data are compared in Table 4-1. Cyclophanes 14 and 15 are fixed antiisomers and show broad emission as well as that of mono-anthophane 13. The emission of mono-naphthophane 12 is quite narrow compared to the others. The absorption and emission spectrum of mono-anthophane 13 have a red shift compared to that of mono-naphthophane 12and bis-naphthophane 14. Wavelength /nm 350400450500550600650 Intensity -0.20.00.20.40.60.81.01.2 12 13 14 15 Figure 4-12 Fluorescence spectra of bridge fluorinated [2.2]cyclophane after normalization. Concentrations in dichloromethane: 12 4.77 10 -5 M; 13 2.83 10 -5 M; 14, 1.20 10 -5 M; 15, 5.79 10 -6 M; silts, 2mm with LG350 filter The absorption of bis-naphthophane 14 is very similar to the case of the non-fluorinated one. 156 The origin of this red shift may derive from the extended

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112 conjugation in 13 and hence different ring distortion. Compared with mono-anthophane 13, both the absorption and emission spectra of bis-anthophane 15 have red shift, which is quite similar to the case of the non-fluorinated parent compound with a vibrational structure in the excite states. 155, 157 Similarly, the other three paracyclophanes also show vibrational emission due to the rigid distorted structure, which led to a greater distance between the two moieties. 155, 156 In the reaction of AF4-yne with -methyl styrene, 24% of the DA product 22 (phenanthopahne) was obtained, and which has a methyl phenanthrene moiety on the paracyclophane instead of anthracene moiety compared to mono-anthophane 13. The change in UV and fluorescence spectra is shown in Figure 4-13 and Figure 4-14, respectively. Spectra of mono-anthophane dimer are also studied with interest. The UV spectrum of dimer 21 is quite similar to that of mono-naphthophane 12 after loss of one aromatic ring in anthracene moiety. Dimer 21 has a big broad absorption form 254 nm to 275 nm, which is centered at 270 nm. The next band is quite similar to that of mono-anthophane 13, while the longest band in mono-anthophane 13 and phenanthophane 22 shrank to a sharp one at 358 nm in dimer 21. There is no absorption after 360 nm compared to the monomer 13 and phenanthophane 22, which may arise from the -* absorption. Basically, the absorption of phenanthophane 22 is the same as that of mono-anthophane 13, except the red shift of the first band in phenanthophane 22 compared to mono-anthophane 13. It may be due to the donating effect of methyl group on the phenanthrene moiety.

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113 F F F F F F F F 22 Wavelength /nm 250300350400450500 2.53.03.54.04.55.0 13 22 12 21 log Figure 4-13 UV spectra in dichloromethane of compound 21 and 22 compared to compound 12 and 13. The emission spectra of mono-anthophane 13, dimer 21, and phenanthophane 22 have a red shift compared to that of mono-naphthophane 12, which has a naphthalenyl instead of an anthracenyl moiety in the cyclophane. It would be interesting to compare the emission spectra of AF4-yne DA products with these bridge fluorinated paracyclophanes. Fluorescence spectra of compounds 23-25 were measured and shown in Figure 4-15. The non-fluorinated parent compound [2.2](1,4)paracyclophane (AH4) was compared with interest.

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114 Wavelength /nm 350400450500550600650 Intensity 0.05.0e+51.0e+61.5e+62.0e+62.5e+63.0e+63.5e+6 12 13 22 21 Figure 4-14 Fluorescence spectra in dichloromethane of compound 21 and 22 compared to compound 12 and 13; 16, 1.2*10 -5 M; 17, 2.15*10 -5 M; slits 2mm with LG350 filter. Emission of AF4 has a 5 nm red shift compared to that of AH4. It is interesting that compound 23 has a stronger fluorescence emission than phenanthophane 22 does, which has an additional phenyl group on one of the cyclophane moieties. This may be due to the Herringbone Heffect in the endo isomer, 93 where the cloud was fixed to the H atoms close to it. The steric hindrance of the endo isomer may also prevent the phenyl ring from deformation in the excited states of 22. Thus, the emission is even weaker than compound 23 which has two additional ethylene groups. All the compounds 22-25 emit at almost the same wavelength, which is not an excimer emission as mentioned above.

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115 F F F F F F F F F F F F F F F F H H H H H H H H 232425AH4 F F F F F F F F Wavelength /nm 400500600 Intensity 01e+62e+63e+64e+65e+66e+6 25 24 23 AF4 AH4 Figure 4-15 Fluoresence of Diels-Alder products in dichloromethane; AH4, 5.77*10 -4 M; AF4, 3.07*10 -4 M; 17, 1.67*10 -4 M; 18, 1.68*10 -4 M; 19, 1.67*10 -4 M; slits 2mm with LG350 filter. All the emission of bridge fluorinated compounds are excited at the with maximum absorption and listed in Table 5-1. The extended conjugation in mono-naphthophane 12 has limited effect on the orbital energy, whereas strained molecules, such as 22, 23 and 24, have better effect on the excited singlet states and ground states.

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116 Table 4-1 Fluorescence spectra data of fluorinated [2.2]paracyclophanes Compounds Concentration (10 -5 M) Excitation (nm) Emission (nm) 12 4.38 310 370 13 2.83 270 455 14 2.48 316 394 15 0.579 275 464 21 1.2 290 460 22 2.15 290 438 23 16.7 290 382 24 16.8 290 385 25 16.7 290 380 AF4 30.7 280 371 AH4 57.7 285 366 4.4 Conclusion In conclusion, four novel bridge fluorinated [2.2]paracyclophanes containing naphthalene and anthracene condensed polycyclic aromatic subunits have been prepared in an efficient one step procedure starting from the readily accessible adducts obtained from the DA reactions of monoor bis arynes of AF4 with benzene and naphthalene. The UV and fluorescence spectra of these cyclophanes were reported. Red shifts of absorption spectra were observed, but no excimer emission was observed in any of the fluorinated [2.2]paracyclophanes. A novel dimerization reaction was observed with mono-anthopahen 13 under the influence of long wavelength irradiation at room temperature and an x-ray diffraction analysis was also obtained. It is anticipated that these novel

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117 compounds will serve as precursors of still more structurally novel [2.2]paracyclophane derivatives. 4.5 Experimental 1H NMR (500 MHz), 13C NMR (125 MHz), and 19F NMR (282 MHz) spectra were recorded using CDCl3 as the solvent, and chemical shifts ( values) were measured relative to the signals for CHCl3, CDCl3, and CFCl3 respectively. Column chromatography was performed using chromatographic silica gel, 200-425 mesh, as purchased from Fisher. All photophysical studies were carried out with solution in 1cm x 1cm quartz cuvettes using dichloromethane solution. For absorption measurements, sample concentration were adjusted to produce Amax <1.0. Absorption spectra were recorded on a Varian Cary 100 dual-beam spectrophotometer. Corrected steady-state emission measurements were performed on a SPEX F-112 fluorimeter. The parameters are set as following: Slits 2.0, filter LG350, integrator 1.0s. 1,1,2,2,11,11,12,12-Octafluoro[2.2]-(1,4)naphthalenoparacyclophane (12); Typical Procedure Adduct 8 (188 mg, 0.44 mmol) was dissolved in pentyl ether (10 mL) and brought to reflux, after which 3,6-dipyridinyltetrazine (129 mg, 0.48 mmol) was added. The solution was maintained at reflux for 2 h after which the solvent was evaporated under vacuum, and the crude product purified via silica gel column chromatography (hexanes-EtOAc, 1:100), to obtain 5 (158 mg, 89%) as a white solid; mp 176-177 C. 1H NMR: = 8.08 (m, 2 H), 7.61 (m, 2 H), 7.45 (s, 2 H), 6.84 (s, 2 H), 6.24 (s, 2 H). 13C NMR = 133.4, 132.1, 131.7, 129.3, 128.9, 127.8, 125.4, 122.7, 119.9, 118.7. 19F

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118 NMR: = -109.21, -114.43 (AB, J = 241.1 Hz, 4 F), -113.34, -114.75 (AB, J = 237.7 Hz, 4 F).MS (EI): m/z = 402 (24) [M+], 226 (100), 176 (47). HRMS (EI): m/z calcd for C20H10F8: 402.0654; found: 402.0650. UV (CH 2 Cl 2 ): max (log ) = 313.0 (3.44), 294.4 (3.33), 259.0 (3.95) nm. Anal. Calcd for C20H10F8: C, 59.71; H, 2.51. Found: C, 59.51; H, 2.27. 1,1,2,2,13,13,14,14-Octafluoro[2.2]-(1,4)anthracenoparacyclophane (13); Typical Procedure Adduct 9 (105 mg, 0.2 mmol) was dissolved in pentyl ether (20 mL) and brought to reflux, after which 3,6-dipyridinyltetrazine (64 mg, 0.23 mmol) was added. The solution was maintained at reflux for 2 h during which it turned pale brown. After the solvent was evaporated under vacuum, the crude product was purified via silica gel column chromatography (hexanes-EtOAc, 1:100), to give 6 (85 mg, 87%) as a yellow solid; mp 230-231 C. 1H NMR: = 8.63 (d, J = 1.8 Hz, 2 H), 8.03 (m, 2 H), 7.61 (m, 2 H), 7.37 (s, 2 H), 6.90 (s, 2 H), 5.90 (s, 2 H).13C NMR: = 133.3, 132.3, 131.4, 129.2, 128.9, 128.8, 128.0, 127.7, 124.7, 123.2, 120.0, 118.7.19F NMR: = -108.86, -110.59(AB, J = 242.8 Hz, 4 F), -113.33, -114.27 (AB, J = 238.0 Hz, 4 F).MS (EI): m/z 452 (21) (M+), 276 (100), 176 (28).HRMS (EI): m/z calcd for C24H12F8: 452.0811; found: 452.0814.UV (CH 2 Cl 2 ): max (log ) = 411.3 (3.26), 386.0 (3.43), 275.0 (4.44) nm. Dimer 21: 1H NMR: 7.60(d, J=8.1Hz, 2H), 7.55(d, J=8.9Hz, 2H), 7.40(ddd, J=8.0, 6.9, 1.2Hz, 4H), 7.33(ddd, J=8.0, 6.8, 1.1Hz, 2H), 7.18(d, J=7.7Hz, 2H), 6.74(dd, J=3.1, 1.5Hz, 2H), 6.36(d, J=8.5Hz, 2H), 6.31(s, 2H), 6.02(d, J=8.4Hz, 2H), 5.70(d, J=8.3Hz, 2H), 4.21(d, J=7.0Hz, 2H); .13C NMR: 134.3, 133.7, 132.4, 131.9, 131.2, 129.8, 129.5,

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119 127.9, 127.6, 129.8, 128.1, 122.7, 128.8, 128.4, 131.6, 128.4, 126.1, 118.0, 118.1, 116.8, 115.0, 50.8, 45.0, 43.2; MS (EI): m/z 452(21), 276(100), 176(49); HRMS (ESI-FT-ICR) Calc for C48H24F16 + Na 927.1515, found 927.1504; UV (CH 2 Cl 2 ): max (log ) =358.1 (3.22), 339.8 (3.64), 323.8 (3.97), 270.6 (4.55) nm. anti-1,1,2,2,11,11,12,12-Octafluoro[2.2](1,4)napthalenophane (14); Typical Procedure Adduct 10 (66 mg, 0.13 mmol) was dissolved in pentyl ether (10 mL) and brought to reflux, after which 3,6-dipyridinyltetrazine (72 mg, 0.27 mmol) was added. The solution was maintained at reflux for 2 h until it turned pale brown. The solvent was then evaporated under vacuum and the crude product purified by recrystallization from CH2Cl2 and hexanes to give product 14 (50.2 mg, 85%) as a white solid; mp 250 C (dec). 1H NMR: = 8.13 (m, 4 H), 7.60 (m, 4 H), 6.41 (s, 4 H). 13C NMR: = 131.6, 129.5, 128.3, 124.9, 124.5, 119.5. 19F NMR: = -107.19, -108.93 (AB, J = 241.11 Hz, 8 F).MS (EI): m/z = 452 (10) [M+], 226 (100). HRMS (EI): m/z calcd for C24H12F8: 452.0811; found: 452.0813. UV (CH 2 Cl 2 ): max (log ) = 319.0 (3.59), 258.0 (3.93) nm. anti-1,1,2,2,13,13,14,14-Octafluoro[2.2]-(1,4)anthracenophane (15); Typical Procedure Adduct 11 (49 mg, 0.08 mmol) was dissolved in pentyl ether (10 mL) and the solution brought to reflux, after which 3,6-dipyridinyl-tetrazine (45 mg, 0.17 mmol) was added. The mixture was maintained at reflux for 2 h until it turned pale brown. The solvent was then evaporated under vacuum and the crude product purified by recrystallization from toluene to give product 15 (50.2 mg, 85%) as a yellow powder.

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120 This compound was sparingly soluble in most solvents and its melting point was above 290 C. 1H NMR; = 8.73 (d, JF,H = 3.1 Hz, 4 H), 8.07 (m, 4 H), 7.60 (m, 4 H), 6.07 (s, 4 H). 19F NMR: = -106.28, -108.82 (AB, J = 234.91 Hz, 8 F). MS (EI): m/z = 552 (13) [M+], 276 (100). HRMS (EI): m/z calcd for C32H16F8: 552.1124; found: 552.1127. UV (CH 2 Cl2): max (log ) = 412 (3.62), 315 (3.73), 303 (3.73), 272 (5.09) nm.

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CHAPTER 5 NOVEL CAGE COMPOUND 5.1 Introduction Pyramidalized alkenes are molecules that contain a carbon-carbon double bond where one or both of the sp 2 hybridized carbons do not lie in the same plane as the four atoms attached to it. 158 Weinshenker and Greens 159 reported the first synthesis of a pyramidalized alkene in 1968, and since then, the synthesis and study of these types of compounds have become a field of active research. These compounds are interesting targets for both synthetic and theoretical organic chemistry because of their intriguing physical properties and fascinating reactivity. 160-162 Pyramidalized alkenes are similar to cis-bending alkynes (benzynes), which are highly reactive. By the calculation, cis-bending acetylene would have 25% greater force constant than that of alkene pyramidalization. Thus, pyramidalized alkenes only have 80% of the strain localized in their double bond compared to the triple bond of benzyne. 158 The LUMO energy is substantially lower in a pyramidalized alkene, but the pyramidalization has little effect on the energy of the HOMO. Thus, the energy gap between the HOMO and LUMO is decreased. In addition, according to frontier orbital theory, the large lowering of LUMO energy should enhance its reactivity toward nucleophiles more than toward electrophiles. Also, the * transition exhibits a red shift. Pyramidalization of a double bond does not just result in classical torsional strain, which favors bond staggering at adjacent carbons. The Olefin Strain Energy (OSE) of a 121

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122 pyramidalized alkene is derived from two sources. 163 One source is the OSE present in the unstrained skeleton of the bicyclic reference olefin; the second source is the pyramidalization of the double bond in the skeleton. The Olefin Pyramidalization Strain Energy (OPSE) is the difference between the OSE of a pyramidalized alkene and that of the appropriate bicyclic reference compound, i.e. the OPSE is part of the OSE. For example, the 6-31G* TCSCF calculated OPSE occupies up to 32% of the total OSE (58.9 kcal/mol) in cubene in reference to bicyclo[2.2.0]hex-1(4)-ene. 163 Figure 5-1 Pyramidalized alkene The double bond in the pyramidalized alkene (Figure 5-1) is weakened due to the decreased overlap between the two -electron clouds. In some sense, the pyramidalization angle correlates with the reactivity of the pyramidalized alkene. Compound 1 (Figure 5-2) has a pyramidalization angle of 24-26 o and reacts readily with triplet oxygens. 158 Compound 3 has an angle of 32.4 o and must be protected by two spiro-cyclopentyl groups. 164 The greatest reported pyramidalization angle was calculated to be 84.1 o in cubene 2. 158 Kuck and Meijiere reported the tribenzo-4,7-dihydroacepentalene derivatives (Figure 5-3), in which the biggest angle between the C1-C10 plane was determined to be 47.2 o by x-ray. 165

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123 123 Figure 5-2 Some pyramidalized alkenes R R 12345678910 Figure 5-3 Tribenzo-4,7-dihydroacepentalene derivative Pyramidalized alkenes are highly reactive and are not easily to generated or handled. Pyramidalized alkenes are usually trapped by Diels-Alder (DA) reactions, and the structures of the starting pyramidalized alkenes are deduced from the adducts. Computation is a common method used in the study of highly pyramidalized alkenes. Most spectroscopic data of pyramidalized alkenes has been obtained by using matrix isolation technology. 166 There is not much data with x-ray diffraction analysis. In the second chapter, the treatment of pseudo-para (4,15) or meta-(4,16) diiodooctatfluoro-[2.2]paracyclophane with strong base potassium t-butoxide in the presence of diene trap was discussed, and high yields of DA adducts derived from 4,5,15,16-bis(dehydro)octafluoro[2.2]paracyclophane 4 (bis-AF4-yne) were obtained (Figure 5-4). When pseudo-ortho(4,13) diiodooctatfluoro-[2.2]paracyclophane was treated under the same conditions, the corresponding 4,5,12,13-bis(dehydro)octafluoro

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124 [2.2]paracyclophane 5, with two arynes on the same side of [2.2]paracyclophane was generated and a highly pyramidalized olefin was generated in the presence of an anthracene diene trap. F F F F F F F F F F F F F F F F 45 Figure 5-4 4,5,15,16-bis(dehydrooctafluoro[2.2]paracyclophane 4 and 4,5,12,13-bis(dehydrooctafluoro[2.2]paracyclophane 5 5.2 Result and Discussions 5.2.1 Synthesis of Cage Compound One third (23%) of the pseudo-ortho-dinitro-AF4 was obtained from the dinitration of AF4 (see chapter 2), which was reduced to the pseudo-ortho-diaminoAF4 and then converted to pseudo-ortho-diiodoAF4 6. The same type of DA reaction was tried under Cram conditions with an anthracene trap. I F2C CF2 CF2 F2C I Potassium t-ButyloxideAnthracene F2C CF2 CF2 F2C 17% CF2 CF2 F2C CF2 CF2 CF2 F2C CF2 4%34%++87Dibutyl ether, reflux6 Figure 5-5 The reaction of the pseudo-ortho-4,12-diiodooctafluoro[2.2]paracyclophane with anthracene

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125 Fortunately, the desired novel cage type of compound 7 was obtained along with the mono-anthracene DA product (34%) after careful chromatographic separation (Figure 5-5). This reaction is not consistent, and the ratio of mono-anthracene adduct to cage product varies from 2:1 to 5:1, and sometimes very little cage product is obtained. F2C CF2 CF2 F2C 6.73125.0127.07.206.67124.6120.9149.4130.8120.8124.47.41139.85.3751.548.35.48150.36.84135.3164.4 CF2 CF2 F2C CF2 CF2 CF2 F2C CF2 O 6.98129.7119.47.11128.5119.4126.5142.951.55.83146.6125.46.77123.87.12143.6125.57.54126.37.165.61135.846.95.35126.3145.2141.6121.77.38131.57.55127.5126.07.306.82123.57.18131.9135.0118.15.10126.6128.7154.582.10.8728.1118.6120.36.63127.86.77128.5127.2119.3149.3149.3128.351.06.02145.67.17124.5126.86.806.80124.87.15124.0145.6143.6142.05.8250.2124.87.53126.67.13125.67.137.48126.6789 Figure 5-6 NMR assignments of pseudo-ortho-diiodoAF4 with anthracene products under Cram conditions Along with the mono-anthracene adduct and the novel cage compound 7, bis-anthracene adduct 8 was obtained in 4% yield. Compound 8 is quite bulky, which comes from the first DA reaction at the 9,10 position followed by a 1,4-addition with another anthracene molecule. When the reaction is carried out under microwave conditions, 10%

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126 of compound 9 was obtained. No compound 9 was detected, which was observed with the conventional heating method. Product 9 is an interesting t-butoxide adduct, which had been observed in the previous AF4-yne with 1-octene reaction under Cram conditions. After the first DA reaction with anthracene, the second aryne was captured by a t-butoxide ion. All the NMR assignments are shown in Figure 5-6. The steric hindrance of the phenyl group from the first DA addition product combined with the bulky base may cause the low yield of the cage compound. Some other bases were tried in order to improve the yield of the cage compound. The results are summarized in Table 5-1. Mono-iodoAF4 was used in these experiments as a model compound instead of ortho-diiodoAF4 because of the difficulty of starting material synthesis. On the basis of these results, it seems that potassium t-butoxide and butyl ether are the best choice. Interestingly, sodium t-butoxide did not work at all in this system, with only aminor change in cation. It is concluded that the heterogeneous KO t Bu system makes the base stronger as discussed in Chapter 3. Table 5-1 Base screening results base solvent Temperature() Results Sodium tert-butoxide(6) Butyl ether 142 No reaction Sodium amide (2) Butyl ether Room No reaction Sodium amide (6) Butyl ether 142 No reaction Sodium ethoxide (5) Butyl ether 142 No reaction Sodium amide (6) DMF Room Reduced AF4 Sodium bis(trimethylsilyl)amide(5) Butyl ether Room Reduced AF4 These reaction conditions will probably lead to the destruction of amides by reacting with the butyl ether.

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127 Microwave conditions show some dramatic effects in organic synthesis compared to conventional heating methodology. 167-169 The ability to rapidly heat and thermally quench by microwave resulted in dramatic increases in the rates and yields of a variety of chemical transformations in organic chemistry. 170-172 It is still unknown why microwaves have such an effect on reaction. The commonly accepted rationale is that microwaves heat mixtures with even and high efficiency. We decided to utilize microwaves to facilitate the formation of the second aryne and force the reaction towards our desired direction. Indeed, the result from the microwave reactor is repeatable, and the average yield of cage compound is much higher than the conventional heating method. We conjecture that microwave heating also increases the starting material collision rates and facilitates attack of the second base. Does high temperature help the formation of the cage product? Trying to improve the yield of the cage compound by increasing the reaction temperature and microwave power proved abortive (Table 5-2). Table 5-2 Solvent effect in the reaction of pseudo-ortho-diIAF4 with anthracene under microwave conditions Solvent Temperature () Time(min) Result(from the 19 F spectrum) Tert-butylbenzene 169 10 cage compound with mixed aryne adducts Decane 175 20 No cage product Butyl ether 142 10 17%Cage compound Pentyl ether 189 10 No cage product N-methyl pyrrolidinone 180 10 No 19 F 2-methoxyethyl ether 180 10 No 19 F Bis[2-(2-methoxy-ethoxy)ethyl] ether 200 10 No 19 F

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128 Several solvents with different boiling points were used and butyl ether was found to be the best one. Increasing reaction temperatures had little effect on the yield of the cage compound. The non-polar solvent, decane, gave no desired product but only the mono-anthracene adduct. t-Butylbenzene gave even more complicated results compared to butyl ether. N-methyl pyrrolidinone, 2-methoxyl ethyl ether, and Bis[2-(2-methoxy-ethoxy)ethyl] ether systems simply destroyed the AF4 compound. Microwave power also had limited impact in the formation of cage product due to steric problems. Besides NMR characterization, a single crystal x-ray diffraction picture demonstrates the structure of the cage compound (Figure 5-7 and Appendix Figure 6). Intuitively, one would expect that less overlap of a cloud would result in a longer bond length. Surprisingly, like other strained olefins, 165 the bond length of the pyramidalized double bond C20-C29 is 1.341(3) a little bit longer than the bond between C17-C18, 1.320(4). Double bonds in the benzene ring C22-C27, C22-C23, C23-C24, and C24-C25 are 1.393(3), 1.388(3), 1.392(4), and 1.372(4) respectively. The C22-C27 bond is much longer than the opposite double bond C24-C25 by 0.02 The bond angles C19-C20-C21, and C30-C29-C28 are 121.40(18) o and 121.86(18) o respectively The average pyramidalization angle (180 o -) is 58.5 o which is the highest value that has ever been observed by x-ray diffraction. The twist angle between the two faces of the four branches of the double bond C19-C30-C20-C29 and C20-C29-C21-C28 is just 34.2 o which is much smaller than the pyramidalization angle. The torsion angle of the two bridges C1-C7-C8-C9 and C4-C15-C16-C12 on the AF4 moiety are almost intact with only 0.73 o and 1.40 o respectively, which indicates no additional steric strain in the AF4 moiety. The two phenyl rings in the AF4 moiety are twisted 13.0 o and 13.2 o toward its perpendicular axis,

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129 respectively. It is noteworthy that in the MS, 526(M + )(EI) is observed with an intensity of 47 percent, the m/e 1052 (EI), dimer of cage compound, is also observed 1/37 compared to its monomer intensity. Figure 5-7 ORTEP drawing of the cage compound (right) and epoxide (left) As mentioned above, the energy gap between the LUMO and HOMO orbitals of pyramidalized double bond decreases with increasing pyramidalization angle. The center double bond should be quite reactive under harsh reaction conditions. However, the cage compound is stable during harsh reaction conditions followed by silica gel chromatography. It is also stable towards molecular oxygen when it is dry, which is quite remarkable in the pyramidalized olefin family. The double bond in tricycle[3.3.2.0 3,7 ]-dec-3(7)-ene 10 (Figure 5-8) 166 is highly reactive towards electrophiles and nucleophiles or [2+2] dimerization. Alkene 10 could only be characterized spectroscopically in an argon matrix, and it dimerizes above 40K. On the other hand, dodecahedradiene 11 can be handed as a crystalline compound at room temperature. 173 The four allylic hydrogens provide sufficient steric protection for the pyramidalization double bond against dimerization. Similarly, the electronic cloud of the benzene ring in 7 and the neighboring double bond around the center double bond may be responsible for the extraordinary stability of its highly pyramidalized double bond.

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130 1011 Figure 5-8 Tricycle[3.3.2.0 3,7 ]-dec-3(7)-ene 10 and dodecahedradiene 11 In similar reactions with benzene and naphthalene as a diene trap for the ortho-bis-AF4-yne under both conventional method and microwave conditions, no desired products were observed except the mono-adducts plus other unknown compounds. 5.2.2 Cage with Triplet Oxygen Nevertheless, the cage product is readily oxidized by triplet oxygen, with half of the cage compounds being oxidized to epoxide 12 in the NMR tube after staying at room temperature for three days (Figure 5-9). Cage compound 7 was also oxidized easily to epoxide 12 during its purification on preparative TLC plates. The carbon signal of the C20-C29 double bond shifted from 164.4ppm in the starting material to 66.4ppm in the epoxide. The 19 F-NMR spectra of the epoxide shifted downfield by 1.65ppm from the cage compound with the same pattern. Fluorine atoms on the substituted side of the molecule coupled with neighboring hydrogens, with the coupling constant being 15.2/12.4 and 15.2/12.1 for epoxide and the cage compound, respectively. F2C CF2 CF2 F2C CDCl3, 3O2room temperature F2C CF2 CF2 F2C O 12 Figure 5-9 Cage compound reaction with oxygen

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131 Increasing the number of double bonds in the sesquinorbornene also increased reactivity toward triplet oxygen. 158 The benzo derivative of compound 1 gave a mixture of epoxide and diketone on exposure to triplet oxygen under conditions where compound 14 (Figure 5-10) failed to react. 174 The neighboring double bond and benzene moieties may also have such an effect on the pyramidalized double bond of 7. 14 Figure 5-10 Syn-sesquinorbornene The crystal X-ray diffraction analysis of the epoxide is illustrated in Figure 5-7 (also Appendix Figure 7). The angles of C17-C30-C29 and C22-C21-C20 are 120.44(12) and 121.06(13), respectively, which are very close to the pyramidilization angle of the central double bond of cage compound 7. In contrast, the dihedral angle between the two corresponding faces widened to 40.7 o (139.3 o ), a little larger than that in the cage compound 7. The torsion angle of the two bridges C4-C7-8-C9 and C12-C15-C16-C1 on the AF4 moiety stayed the same, 0.44 o and 2.80 o respectively, while the twist angle of two phenyl rings changed to 12.7 o and 13.1 o respectively. 5.2.3 Cage with Chlorine When oxygen is bubbled into the deuterated chloroform solution slowly at room temperature, another compound appeared in the 19 F NMR. The ratio of this compound to epoxide varied from 1.3:1 to 2.6:1. This variation might due to the different concentration of substrate and different oxygen bubbling speed. 174 The yield of the epoxide was 21%

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132 whereas that of the new compound was 52%. This compound turned out to be the chlorine adduct 13 (Figure 5-11). The pyramidalized double bond signal at 164.4 ppm in the cage compound disappeared in the 13 C NMR, and a new signal at 78.3 ppm appeared, which is similar, but different from the epoxide signal at 66.4 ppm. F2C CF2 F2C CF2 F2C CF2 F2C CF2 Cl Cl CDCl3room temperaturesaturated 3O213 F2C CF2 F2C CF2 +1252%21%O Figure 5-11 Bubbling oxygen through the solution of cage compound Pure chloroform is known to be decomposed by air, especially when at high oxygen levels. 175, 176 The mechanism is shown below. 4CHCl 3 + 4O 2 = 4COCl 2 + 2H 2 O + Cl 2 2COCl 2 + 2H 2 O= 2 CO 2 + 4HCl We believe that this chlorine product was trapped by the highly reactive double bond under the reaction conditions, which led to the final product. This reaction is analogous to the cage compound reaction with bromine. The dihedral angle between C26-C29-C25-C30 and C24-C17-C25-C30 is 54.0 o which is much bigger than that of the cage compound and the epoxide. The strain is thus further released in the dichloride adduct. 5.2.4 Cage with Singlet Oxygen In a study of the reaction of singlet oxygen with olefin, 177 a dioxetane was obtained in 81% yield along with 19% of epoxide product. The reaction was hypothesized to

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133 proceed through a perepoxide intermediate (Figure 5-12), which could be trapped successfully with pinacolone to give epoxide and t-butyl acetate. Paquette et al reported an interesting reaction of pyramidalized alkene 14 with singlet oxygen. 174 The rigid framework excluded the possibility of 2S+2A cycloaddition with singlet oxygen. However, when the reaction was carried out in benzene with rose Bengal as a sensitizer, a mixture of epoxide and diketone in a 1:3 ratio was obtained. O O hv, O2sensitizerpinacolone AdAdO O O O O O + 81%19% Figure 5-12 Trapping the intermediate of the reaction of singlet oxygen with pyramidalized alkene Our cage compound was subjected to singlet oxygen (Figure 5-13) generated via the published method. 178, 179 A CDCl 3 solution of cage compound (3 mg)in a NMR tube was added rose Bengal (5 mg) and immersed into a flowing cooling water bath to keep the vessel at room temperature. Oxygen was bubbled into the solution through a long metal needle while the solution was irradiated through a 0.05M K 2 Cr 2 O 7 solution filter. The reaction was complete after 5 hours of irradiation with a 250W Sylavi mercury lamp. Epoxide 12 and diketone 15 were obtained in 66% and 33% (2:1 ratio), respectively, by NMR characterization. Assignments of 1 H and 13 C are shown in Figure 5-12. The carbon signal at 193.7 explicitly indicates the existence of carbonyl group. The chemical shifts of

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134 protons in the AF4 moiety shifted to 7.26/7.25 ppm from that of 6.73/6.67 ppm in cage compound 7, and the chemical shifts of olefin protons moved up field by 0.99 ppm from that of 6.84 ppm in cage compound. F2C CF2 F2C CF2 F2C CF2 F2C CF2 O O CDCl3room temperatureO2, Rose Bengal15 F2C CF2 F2C CF2 +1266%33%O hv F2C CF2 F2C CF2 O O 193.7127.55.85136.3120.77.26130.3135.4130.27.25120.7135.6136.356.25.68131.2129.37.58128.77.2954.55.0915 Figure 5-13 Compound 14 and cage with singlet oxygen product 15 5.2.5 Cage with Bromine When bromine was added to the cage compound solution in carbon tetrachloride at 0 the red brown color of bromine disappeared immediately, and a dibromide adduct 16 was obtained quantitatively. The C20-C29 carbon signal shifted from 164.4 ppm in the pyramidalized double bond to 74.9 ppm in the bromine adduct, which is different from that of 66.4 ppm in expoxide and 78.3 ppm in dichloride.

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135 F2C CF2 F2C CF2 CCl40oC F2C CF2 F2C CF2 16100% Br2, 1 equiv.Br Br Figure 5-14 Reaction of cage with bromine 5.3 Conclusion An unusual reaction of pseudo-ortho-4,12 diiodooctafluoro[2.2]paracyclophane with base potassium t-butoxide and anthracene led to the novel highly reactive pyrimidalized alkene, which is stable in moist and oxygen at room temperature. This cage compound reacts slowly with triplet oxygen to give epoxide, while the diketone can be obtained with singlet oxygen. 5.4 Experimental General Methods. 1 H (500 MHz), 13 C (126 MHz), and 19 F (282 MHz) NMR spectra were recorded using CDCl 3 as the solvent, and chemical shifts ( values) were measured relative to the signals for CHCl 3 CDCl 3 and CFCl 3 respectively. 1 H and 13 C chemical shift data are directly indicated on the structures of the adducts in the Results and Discussion section above, whereas 19 F NMR data are provided in the Experimental Section below. X-ray crystal analyses were performed by the Center for X-ray Crystallography and HRMS and CH micro elemental analyses by the Spectroscopic Services Group at the University of Florida. Column chromatography was performed using chromatographic silica gel, 200-425 mesh, as purchased from Fisher, unless

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136 otherwise mentioned. Discover microwave from CEM Company with an output frequency of 2450 MHz is used in all microwave reactions. Photooxygenation was performed with a 250W Sylavi mercury lamp. The output of the lamp was filtered with 0.05M K 2 Cr 2 O 7 solution to remove light below 460 nm. The photolysis was carried out in NMR tubes with outside water flow to keep the temperature around 25. Oxygen was bubbled through the solution being photooxygenated via a metal needle. 4,12-Dinitro-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophanes. See chapter 2 experimental. 4,12-Diamino-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophanes. See chapter 2 experimental. 4,12-Diiodo-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophanes, 51 A solution of 4,12-diaminooctafluoro[2.2]paracyclo-phanes (5.0 g, 13 mmol) in acetic acid (10 mL) was cooled to 0 in an ice/brine bath; ice (5 mL) and concentrated sulfuric acid (5 mL) were added with stirring. With the temperature maintained below 0 sodium nitrite (5.0 g, 72.0 mmol) was added as quickly as possible to the solution in one batch. The reaction was stirred at this temperature for 2 h, and then the mixture was poured into an aqueous solution (10 mL) of potassium iodide (13 g, 77 mmol) at room temperature with vigorous stirring. This mixture was kept stirring at room temperature overnight and then filtered. The solid was purified by column chromatography (hexane/ethyl acetate, 50:1) to give 4.98 g (63%) product.

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137 Generation of 4,5,12,13-Bis(dehydro)octafluoro[2.2]paracyclophane, 1, and its Reaction with [2.2]Paracyclophane. Into a three necked round flask were charged with pseudo-ortho-diiodo AF4 (0.12 g, 0.2mmol), anthracene (78mg, 2.2mmol), and potassium t-butoxide (0.23g, 2.0mmol) followed by 10ml butyl ether. The mixture was then refluxed for 30 minutes. 19F NMR showed no starting material. The mixture was allowed to cool down and filtered through a short pad of silicon gel, and washed with 3x10 ml dichloromethane. Solvent was evaporated under vacuum, and the products were further purified through silicon gel column. Product No1 is the same product as AF4-yne with anthracene reaction (34%); product No2 is cage compound 7 with a 17% yield; The next product is pseudo-ortho-bisanthracene adduct 8 (4%), and product 9 (10%) was obtained from the microwave reaction as described below. Microwave reaction procedure: into a 50ml one neck-round flask was charged with pseudo-ortho-diiodo AF4 (0.12 g, 0.2mmol), anthracene (78mg, 2.2mmol), and potassium t-butoxide (0.23g, 2.0mmol) followed by 10ml butyl ether. The mixture was degassed with vacuum pump three times. A nitrogen balloon was attached to the reaction vessel, which was put into the microwave reactor with care. The parameters were set as following: heating model, standard; solvent, dimethyl sulfoxide; no pressure; power, 180W; temperature, 150; runtime, 20minutes; hold time, 20minutes; stirrer, on; cooling, on. The spectra of cage compound 7 are: 1 H NMR (300MHz, CDCl 3 /TMS) : 7.41(d, J= 5.7Hz, 1H), 7.38(d, J=5.4Hz, 1H) 7.20(dd, J= 5.4, 3Hz 2H), 6.82(dd, J=4.5, 3Hz, 2H), 6.71(s, 2H), 6.66(s, 2H), 5.71(s, 2H), 5.48(dd, J=4.2, 3.6Hz, 2H); 13 C NMR (126MHz, CDCl 3 ) 164.4, 150.3, 149.4, 139.8, 135.3, 130.8, 130.8, 127.0, 125.0, 124.6, 124.4,

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138 120.9, 120.8, 51.5, 48.3; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -104.20(d, J=243.9 Hz, 2F), -104.55(d, J=243.9 Hz, 2F), -107.59(dd, J=242.2, 12.1Hz, 2F), -108.0(dd, J=242.2, 15.2Hz, 2F). IR (cm -1 ) 3076, 3034, 2966, 2868, 1954, 1916, 1810, 1706, 1658, 1601, 1474, 1454, 1378, 1268, 1150, 1117; MS (EI) m/z 1052(2M + ), 526(47)[M + ], 352(10), 300(100), 276(11), 250(95); HRMS Calc for C 30 H 14 F 8 526.0968, found 526.0967(EI); UV (CH 2 Cl 2 ) max 328, 309, 246nm. The spectra of 8 are: 1 H NMR (500MHz, CDCl 3 /TMS) : 7.55(dd, J=4.1, 3.4Hz, 2H), 7.54(t, J=3.2Hz, 2H), 7.38(s, 2H), 7.30(m, 2H), 7.16(m, 2H), 7.12(m, J=, 2H), 7.11(s, 2H), 6.98(s, 2H), 6.77(m, J=, 2H), 5.83(d, J=2.6Hz, 2H), 5.61(m, 2H), 5.35(m, 2H); 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) : -111.18, -116.35(AB, J=250.13 Hz, 4F), -113.72, -117.05 (AB, J=250.13 Hz, 4F); 13 C NMR (126MHz, CDCl 3 ) : 146.6, 145.2, 143.6, 142.9, 141.6, 135.8, 131.5, 129.7, 128.5, 127.5, 126.5, 126.3, 126.3, 126.0, 125.5, 125.4, 123.8, 121.7, 119.4, 119.4, 51.5, 46.9. MS (EI) m/z: 705 (30), 704(74)[M + ], 352(49), 180(23), 178(52), 149(30), 77(100), HRMS: Calc for C 44 H 24 F 8 :704.1750, Found: 704.1765 (EI) Spectra of compound 9 are: 1 H NMR (500MHz, CDCl 3 /TMS) 7.53(m, 1H), 7.48(dt, J=5.0, 2.5Hz, 1H), 7.17(m, 2H), 7.13(m, 2H), 6.82(d, J=7.9Hz, 1H), 6.80(ddd, J=6.2, 3.7, 1.2Hz, 1H), 6.77(d, J=9.4Hz, 1H), 6.63(dd, J=8.1Hz, 1H), 6.01(d, J=2.0Hz, 1H), 5.82(s, 1H), 5.10(s, 1H), 0.87(s, 9H); 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) : -106.95, -116.18(AB, J=240.83Hz, 2F), -109.25, -111.99 (AB, J=241.11Hz, 2F), -115.19, -116.10(AB, J=214.96Hz, 2F), -117.95, -119.03(AB, J=240.83Hz, 2F); 13 C NMR (126MHz, CDCl 3 ) : 154.5, 145.6, 145.0, 144.3, 144.3, 143.6, 142.0, 135.0, 131.9, 128.7, 128.5, 128.3, 127.8, 127.2, 126.8, 126.8, 126.6, 126.0, 125.6, 124.8, 124.8, 124.5, 124.0,

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139 123.5, 120.3, 119.3, 118.6, 118.1, 82.1, 51.0, 50.2, 28.1; MS(EI) m/z 600(M + )(0.67), 585(3), 544(100), 353(21), 352(84); HRMS Calc. for C 34 H 24 F 8 O 600.1699, Found 600.1713 (EI). Reaction of cage compound with triplet oxygen: cage compound (6mg, 0.01mmol) in 5mm NMR tube with 0.5 ml CDCl 3 was placed at room temperature for three days, NMR showed that half cage compound was oxidized to epoxide. No other product was detected. 1 H NMR (500MHz, CDCl 3 /TMS) : 7.23(m, 2H), 7.17(m, 2H), 6.91(s, 2H), 6.89(s, 2H), 6.34(m, 2H), 5.41(s, 2H), 5.14(t, J=3.9 Hz, 2H); 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) : -105.85, -109.88(AB, J=240.83Hz, 4F), -106.34, -110.38 (AB, J=243.93Hz, 4F), the coupling with proton adjacent is 15.2, and 12.4Hz; 13 C NMR (126MHz, CDCl 3 ) : 147.8, 147.7, 137.9, 132.5, 132.4, 132.3, 127.5, 127.3, 127.2, 124.9, 120.9, 120.8, 66.4, 45.0, 41.4; MS(EI) m/z 542(M + )(22), 514(100), 288(47), 226(20); HRMS Calc. for C 32 H 14 F 8 O 542.0917, Found 542.0916 (EI); UV (CH 2 Cl 2 ) max 330, 290, 280. Reaction of cage compound with bromine: cage compound (3.4mg, 0.006mmol) in 10ml round flask with 5 ml CCl 4 was placed in an ice bath. Bromine (1 mg, 0.33l, 0.0063mmol) was added through 1l syringe at a time and the red-brown color disappeared immediately after the addition. The mixture was stirred at this temperature for another 5 minutes, and then solvent was evaporated under vacuum. Pure bromine adduct 16 (100%) was obtained without further purification. 1 H NMR (500MHz, CDCl 3 /TMS) 7.23(m, 2H), 7.10(m, 2H), 6.89(s, 2H), 6.87(s, 2H), 6.66(m, 2H), 5.46(s, 2H), 5.33(m, 2H); 13 C NMR (126MHz, CDCl 3 ) 142.5, 141.8, 140.6, 138.1, 132.6, 132.5, 128.2, 127.9, 127.4, 127.2, 120.4, 74.9, 55.1, 50.9; 19 F NMR (282MHz, CDCl 3 /CFCl 3 )

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140 -107.36, -112.21(AB, J=240.83Hz, 4F), -107.46, -112.46(AB, J=243.93Hz, 4F), the splitting of fluorine by proton are 12.13 and 10.72 respectively. MS(EI) m/z 687(19), 685(36), 683(16), 526(21), 352(10), 276(23), 226(19), 149(100); HRMS Calc. for C 30 H 14 Br 2 F 8 683.9334, Found 683.9341 (EI); UV (CH 2 Cl 2 ) max 330, 291, 282. Reaction of cage compound with saturated triplet oxygen: oxygen was bubbled into 0.5 ml CDCl 3 solution of cage compound (5.6mg, 0.01mmol) in 5mm NMR tube at room temperature over night. Yields were determined by internal standard ,,trifluoromethyl toluene by 19 F NMR. The mixture was separated by preparative TLC plates after the starting material was completely consumed. Epoxide and chlorine adducts were obtained in 21% and 52% yield respectively. 1 H NMR (500MHz, CDCl 3 /TMS) 7.23(m, 2H), 7.09(m, 2H), 6.89(s, 2H), 6.88(s, 2H), 6.65(, m, 2H), 5.30(s, 2H), 5.16(m, 2H); 13 C NMR (126MHz, CDCl 3 ) 142.7, 142.1, 139.5, 137.0, 132.6, 128.1, 127.9, 127.5, 120.t5, 120.4, 78.3, 54.4, 50.3; 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -107.43, -112.21(AB, J=243.93Hz, 4F), -107.53, -112.47(AB, J=241.1Hz, 4F), the splitting of fluorine by proton is 12.13, 15.23Hz respectively. MS(EI) m/z 598(25), 597(11), 596(M + )(37), 370(100), 276(33), 226(28), 149(44); HRMS Calc. for C 30 H 14 Cl 2 F 8 596.0345, Found 596.0353 (EI). Photooxygenation of cage: a 0.5 ml CDCl 3 solution of cage compound (3 mg, 0.006mmol) containing rose Bengal (5 mg) was immersed into a flow-cooling water bath to keep vessel at room temperature. Oxygen was bubbled into the solution through a long metal needle while the solution is irradiated by a 250W Sylavi mercury lamp through a 0.05M K 2 Cr 2 O 7 solution filter. Reaction is complete after 5 h with 66% of epoxide and 33% of diketone obtained. The products were separated by preparative silica gel TLC

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141 plates. Diketone 15: 1 H NMR (500MHz, CDCl 3 /TMS) 7.58(m, 2H), 7.29(m, 2H), 7,26(s, 2H), 7.25(s, 2H), 5.85(d, J=4.5Hz, 2H), 5.68(s, 2H), 5.09(d, J=3.6Hz, 2H); 19 F NMR (282MHz, CDCl 3 /CFCl 3 ) -106.16(d, J=250.1Hz, 2F), -106.18(d, J=249.0Hz, 2F), -109.73(d, J=240.8Hz, 2F), -110.26(d, J=241.7Hz, 2F). The coupling constant CFH is 19.4Hz; 13 C NMR (126MHz, CDCl 3 ) 193.7, 136.3, 136.3, 135.6, 135.4, 131.2, 130.2, 130.3, 129.3, 128.7, 127.5, 120.7, 120.7, 56.2, 54.5; MS (EI) m/z 558 (M + )(3), 276(100), 226(63); HRMS Calc for C 30 H 14 O 2 F 8 558.0866, Found 558.0892 (EI).

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APPENDIX X-RAY DATA Figure 1: X-ray of octafluoro[2.2]parcyclophane aryne with [2.2]paractclophane adduct 142

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143 Table 1. Crystal data and structure refinement for yz02. Identification code yz02 Empirical formula C32 H22 F8 Formula weight 558.50 Temperature 193(2) K Wavelength 0.71073 Crystal system Triclinic Space group P-1 Unit cell dimensions a = 7.4353(4) = 104.106(1). b = 11.4074(5) = 97.453(1). c = 15.4130(7) = 104.071(1). Volume 1204.8(1) 3 Z 2 Density (calculated) 1.540 Mg/m3 Absorption coefficient 0.132 mm-1 F(000) 572 Crystal size 0.32 x 0.19 x 0.12 mm3 Theta range for data collection 1.39 to 27.49. Index ranges -9h9, -14k14, -20l19 Reflections collected 10991 Independent reflections 5421 [R(int) = 0.0275] Completeness to theta = 27.49 98.0 % Absorption correction Integration Max. and min. transmission 0.9872 and 0.9563 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 5421 / 0 / 361 Goodness-of-fit on F2 1.026 Final R indices [I>2sigma(I)] R1 = 0.0467, wR2 = 0.1173 [4305] R indices (all data) R1 = 0.0600, wR2 = 0.1264 Largest diff. peak and hole 0.308 and -0.246 e.-3 R1 = (||Fo| |Fc||) / |Fo| wR2 = [w(Fo2 Fc2)2] / wFo22]]1/2 S = [w(Fo2 Fc2)2] / (n-p)]1/2 w= 1/[2(Fo2)+(0.0540*p) 2 +0.61*p], p = [max(Fo2,0)+ 2* Fc2]/3

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144 Figure 2 : X-ray of octafluoro[2.2]parcyclophane aryne with anthracene adduct

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145 Table 2. Crystal data and structure refinement for yz03. Identification code yz03t Empirical formula C28 H16 F8 Formula weight 504.41 Temperature 193(2) K Wavelength 0.71073 Crystal system Triclinic Space group P-1 Unit cell dimensions a = 8.9041(5) = 101.308(1). b = 9.3253(5) = 91.161(1). c = 14.3897(8) = 107.872(1). Volume 1110.9(1) 3 Z 2 Density (calculated) 1.508 Mg/m3 Absorption coefficient 0.134 mm-1 F(000) 512 Crystal size 0.23 x 0.11 x 0.10 mm3 Theta range for data collection 1.45 to 27.50. Index ranges -11h11, -12k12, -18l18 Reflections collected 10130 Independent reflections 5004 [R(int) = 0.0331] Completeness to theta = 27.50 97.9 % Absorption correction Integration Max. and min. transmission 0.9915 and 0.9717 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 5004 / 0 / 343 Goodness-of-fit on F2 1.066 Final R indices [I>2sigma(I)] R1 = 0.0413, wR2 = 0.1035 [3846] R indices (all data) R1 = 0.0598, wR2 = 0.1162 Largest diff. peak and hole 0.299 and -0.237 e.-3 R1 = (||Fo| |Fc||) / |Fo| wR2 = [w(Fo2 Fc2)2] / wFo22]]1/2 S = [w(Fo2 Fc2)2] / (n-p)]1/2 w= 1/[2(Fo2)+(0.0464*p) 2 +0.55*p], p = [max(Fo2,0)+ 2* Fc2]/3

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146 Figure 3 : X-ray of octafluoro[2.2]parcyclophane aryne with furan adduct:exo isomer

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147 Table 3. Crystal data and structure refinement for yz04. Identification code yz04 Empirical formula C20 H10 F8 O Formula weight 418.28 Temperature 193(2) K Wavelength 0.71073 Crystal system Trigonal Space group P3(2)21 Unit cell dimensions a = 9.2358(4) = 90. b = 9.2358(4) = 90. c = 33.198(2) = 120. Volume 2452.4(2) 3 Z 6 Density (calculated) 1.699 Mg/m3 Absorption coefficient 0.167 mm-1 F(000) 1260 Crystal size 0.19 x 0.11 x 0.08 mm3 Theta range for data collection 1.84 to 27.50. Index ranges -11h12, -11k12, -42l42 Reflections collected 21640 Independent reflections 3743 [R(int) = 0.0437] Completeness to theta = 27.50 100.0 % Absorption correction Integration Max. and min. transmission 0.9874 and 0.9725 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3743 / 0 / 265 Goodness-of-fit on F2 1.080 Final R indices [I>2sigma(I)] R1 = 0.0424, wR2 = 0.0929 [3036] R indices (all data) R1 = 0.0583, wR2 = 0.1029 Absolute structure parameter 0.3(7) Extinction coefficient 0.0082(8) Largest diff. peak and hole 0.345 and -0.372 e.-3 R1 = (||Fo| |Fc||) / |Fo| wR2 = [w(Fo2 Fc2)2] / wFo22]]1/2 S = [w(Fo2 Fc2)2] / (n-p)]1/2 w= 1/[2(Fo2)+(0.0350*p) 2 +1.31*p], p = [max(Fo2,0)+ 2* Fc2]/3

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148 Figure 4: X-ray of octafluoro[2.2]parcyclophane bisaryne with naphtahlene adduct

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149 Table 4. Crystal data and structure refinement for yz09. Identification code yz09 Empirical formula C36 H20 F8 Formula weight 604.52 Temperature 193(2) K Wavelength 0.71073 Crystal system Triclinic Space group P-1 Unit cell dimensions a = 12.4437(7) = 87.693(2). b = 13.2605(7) = 78.725(2). c = 17.485(2) = 64.870(2). Volume 2558.8(2) 3 Z 4 Density (calculated) 1.569 Mg/m3 Absorption coefficient 0.131 mm-1 F(000) 1232 Crystal size 0.24 x 0.19 x 0.11 mm3 Theta range for data collection 1.19 to 27.50. Index ranges -8h16, -16k17, -21l22 Reflections collected 17002 Independent reflections 11267 [R(int) = 0.0266] Completeness to theta = 27.50 95.9 % Absorption correction Analytical Max. and min. transmission 0.9888 and 0.9607 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 11267 / 0 / 793 Goodness-of-fit on F2 1.017 Final R indices [I>2sigma(I)] R1 = 0.0394, wR2 = 0.0963 [8161] R indices (all data) R1 = 0.0617, wR2 = 0.1062 Largest diff. peak and hole 0.304 and -0.223 e.-3 R1 = (||Fo| |Fc||) / |Fo| wR2 = [w(Fo2 Fc2)2] / wFo22]]1/2 S = [w(Fo2 Fc2)2] / (n-p)]1/2 w= 1/[2(Fo2)+(0.522*p) 2 +0.4421*p], p = [max(Fo2,0)+ 2* Fc2]/3

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150 Figure 5: X-ray of octafluoro[2.2]parcyclophane ortho-bis-aryne with anthracene adduct

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151 Table 5. Crystal data and structure refinement for yz17. Identification code yz17 Empirical formula C30 H14 F8 Formula weight 526.42 Temperature 173(2) K Wavelength 0.71073 Crystal system Monoclinic Space group P2(1)/n Unit cell dimensions a = 9.3031(5) = 90. b = 14.1979(8) = 104.872(2). c = 16.3548(9) = 90. Volume 2087.9(2) 3 Z 4 Density (calculated) 1.675 Mg/m3 Absorption coefficient 0.147 mm-1 F(000) 1064 Crystal size 0.27 x 0.19 x 0.17 mm3 Theta range for data collection 1.93 to 27.50. Index ranges -10<=h<=12, -18<=k<=18, -20<=l<=21 Reflections collected 13606 Independent reflections 4738 [R(int) = 0.0405] Completeness to theta = 27.50 98.8 % Absorption correction Integration Max. and min. transmission 0.9781 and 0.9633 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4738 / 0 / 419 Goodness-of-fit on F2 1.177 Final R indices [I>2sigma(I)] R1 = 0.0599, wR2 = 0.1303 [4088] R indices (all data) R1 = 0.0700, wR2 = 0.1355 Largest diff. peak and hole 0.351 and -0.268 e.-3 R1 = (||Fo| |Fc||) / |Fo| wR2 = [w(Fo2 Fc2)2] / wFo22]]1/2 S = [w(Fo2 Fc2)2] / (n-p)]1/2 w= 1/[2(Fo2)+(0.0540*p) 2 +0.61*p], p = [max(Fo2,0)+ 2* Fc2]/3

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152 Figure 6: X-ray of octafluoro[2.2]parcyclophane ortho-bis-aryne with anthracene adduct epoxide

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153 Table 6. Crystal data and structure refinement for yz20. Identification code yz20 Empirical formula C30 H14 F8 O Formula weight 542.41 Temperature 173(2) K Wavelength 0.71073 Crystal system Monoclinic Space group P2(1)/n Unit cell dimensions a = 9.2818(7) = 90. b = 14.745(2) = 105.490(2). c = 15.9431(11) = 90. Volume 2102.8(3) 3 Z 4 Density (calculated) 1.713 Mg/m3 Absorption coefficient 0.152 mm-1 F(000) 1096 Crystal size 0.32 x 0.20 x 0.19 mm3 Theta range for data collection 1.91 to 28.03. Index ranges -12h12, -19k19, -21l20 Reflections collected 18286 Independent reflections 4929 [R(int) = 0.0332] Completeness to theta = 28.03 97.0 % Absorption correction Integration Max. and min. transmission 0.9750 and 0.9590 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4929 / 0 / 352 Goodness-of-fit on F2 1.060 Final R indices [I>2sigma(I)] R1 = 0.0430, wR2 = 0.1149 [4138] R indices (all data) R1 = 0.0517, wR2 = 0.1206 Largest diff. peak and hole 0.320 and -0.285 e.-3 R1 = (||Fo| |Fc||) / |Fo| wR2 = [w(Fo2 Fc2)2] / wFo22]]1/2 S = [w(Fo2 Fc2)2] / (n-p)]1/2 w= 1/[2(Fo2)+(m*p) 2 +n*p], p = [max(Fo2,0)+ 2* Fc2]/3, m & n are constants.

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154 Figure 7: X-ray of octafluoro[2.2]parcyclophane ortho-bis-aryne with anthracene adduct dichloride

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155 Table 7. Crystal data and structure refinement for yz25. Identification code yz25 Empirical formula C30 H16 Cl2 F8 Formula weight 1797.98 Temperature 173(2) K Wavelength 0.71073 Crystal system Triclinic Space group P1 Unit cell dimensions a = 9.2819(5) = 83.289(1). b = 9.7160(6) = 80.492(1). c = 21.2585(12) = 64.244(1). Volume 1700.78(17) 3 Z 3 Density (calculated) 1.755 Mg/m3 Absorption coefficient 0.374 mm-1 F(000) 906 Crystal size 0.20 x 0.14 x 0.08 mm3 Theta range for data collection 0.97 to 27.50. Index ranges -11h12, -12k12, -27l27 Reflections collected 15109 Independent reflections 13236 [R(int) = 0.0284] Completeness to theta = 27.50 96.4 % Absorption correction Integration Max. and min. transmission 0.9723 and 0.9254 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 13236 / 3 / 1081 Goodness-of-fit on F2 0.913 Final R indices [I>2sigma(I)] R1 = 0.0602, wR2 = 0.1575 [11283] R indices (all data) R1 = 0.0688, wR2 = 0.1664 Absolute structure parameter -0.01(5) Largest diff. peak and hole 1.295 and -0.682 e.-3 R1 = (||Fo| |Fc||) / |Fo| wR2 = [w(Fo2 Fc2)2] / wFo22]]1/2 S = [w(Fo2 Fc2)2] / (n-p)]1/2 w= 1/[2(Fo2)+(m*p) 2 +n*p], p = [max(Fo2,0)+ 2* Fc2]/3, m & n are constants.

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156 Figure 8 X-ray of dimer of anthraceno[2.2]parcyclophane 12

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157 Table 8. Crystal data and structure refinement for yz27. Identification code yz27 Empirical formula C97.50 H51 Cl3 F32 Formula weight 1936.73 Temperature 173(2) K Wavelength 0.71073 Crystal system Triclinic Space group P-1 Unit cell dimensions a = 10.4307(6) = 77.937(2). b = 19.5561(11) = 84.115(2). c = 19.6381(11) = 87.310(2). Volume 3895.4(4) 3 Z 2 Density (calculated) 1.651 Mg/m3 Absorption coefficient 0.248 mm-1 F(000) 1950 Crystal size 0.21 x 0.10 x 0.09 mm3 Theta range for data collection 1.07 to 27.50. Index ranges -13h12, -21k25, -25l25 Reflections collected 25923 Independent reflections 17167 [R(int) = 0.0362] Completeness to theta = 27.50 95.8 % Absorption correction Integration Max. and min. transmission 0.9805 and 0.9508 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 17167 / 0 / 1180 Goodness-of-fit on F2 0.787 Final R indices [I>2sigma(I)] R1 = 0.0415, wR2 = 0.0900 [8451] R indices (all data) R1 = 0.0919, wR2 = 0.0969 Largest diff. peak and hole 0.354 and -0.475 e.-3 R1 = (||Fo| |Fc||) / |Fo| wR2 = [w(Fo2 Fc2)2] / wFo22]]1/2 S = [w(Fo2 Fc2)2] / (n-p)]1/2 w= 1/[2(Fo2)+(m*p) 2 +n*p], p = [max(Fo2,0)+ 2* Fc2]/3, m & n are constants.

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161 38 Kaupp, G.; Zimmermann, I., Intramolecular 4+4 Photocycloaddition of 2.2 (1,4)-Naphthalenophane. Angewandte Chemie-International Edition in English 1976, 15, (7), 441-442. 39 Fratini, A. V., Crystal Structures of 2 Novel Polycyclic Products C26h26o2 and C24h10, from Photolysis of Anti2.2 Paracyclonaphthane. Journal of the American Chemical Society 1968, 90, (7), 1688-&. 40 Becker, B.; Bohnen, A.; Ehrenfreund, M.; Wohlfarth, W.; Sakata, Y.; Huber, W.; Mullen, K., Ions Derived from Dianthrylethane Species How the Mode of Linking Affects the Intramolecular Electron-Transfer. Journal of the American Chemical Society 1991, 113, (4), 1121-1127. 41 Morisaki, Y.; Chujo, Y., Novel 2.2 Paracyclophane-Fluorene-Based Conjugated Copolymers: Synthesis, Optical, and Electrochemical Properties. Macromolecules 2004, 37, (11), 4099-4103. 42 Hiyama, T., Organofluorine Compounds: Chemistry and Applications. ed.; Springer: New York, 2000. 43 Dolbier, W. R.; Rong, X. X.; Xu, Y. L.; Beach, W. F., A New and Practical Synthesis of Octafluoro 2.2 Paracyclophane. Journal of Organic Chemistry 1997, 62, (21), 7500-7502. 44 Dolbier, W. R.; Duan, J. X.; Roche, A. J., A Novel, Non-High-Dilution Method for Preparation of 1,1,2,2,9,9,10,10-Octafluoro 2.2 Paracyclophane. Organic Letters 2000, 2, (13), 1867-1869. 45 Dolbier, W. R.; Asghar, M. A.; Pan, H. Q.; Celewicz, L., A New Synthesis of Octafluoro 2.2 Paracyclophane. Journal of Organic Chemistry 1993, 58, (7), 1827-1830. 46 Chow, S. W.; Pilato, L. A.; Wheelwri.Wl, Synthesis of 1,1,2,2,9,9,10,10-Octafluoro 2.2!Paracyclophane. Journal of Organic Chemistry 1970, 35, (1), 20-&. 47 Dolbier, W. R.; Duan, J. X.; Abboud, K.; Ameduri, B., Synthesis and Reactivity of a Novel, Dimeric Derivative of Octafluoro 2.2 Paracyclophane. A New Source of Trifluoromethyl Radicals. Journal of the American Chemical Society 2000, 122, (49), 12083-12086. 48 Dolbier, W. R.; Beach, W. F., Parylene-AF4: a Polymer with Exceptional Dielectric and Thermal Properties. Journal of Fluorine Chemistry 2003, 122, (1), 97-104.

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172 163 Hrovat, D. A.; Borden, W. T., Abinitio Calculations of the Olefin Strain Energies of Some Pyramidalized Alkenes. Journal of the American Chemical Society 1988, 110, (14), 4710-4718. 164 Paquette, L. A.; Shen, C. C.; Krause, J. A., Isodicyclopentadienes and Related Molecules .47. A Shelf-Stable Syn-Sesquinorbornatriene an Extreme Example of a Crystallographically Determined Pi-Pyramidalization Angle. Journal of the American Chemical Society 1989, 111, (6), 2351-2352. 165 Haag, R.; Ohlhorst, B.; Noltemeyer, M.; Schuster, A.; Kuck, D.; Demeijere, A., Structural and Chemical-Properties of Tribenzo-4,7-Dihydroacepentalene Derivatives and Their Central Pyramidalised Double-Bonds. Journal of the Chemical Society-Chemical Communications 1993, (23), 1727-1728. 166 Radziszewski, J. G.; Yin, T. K.; Miyake, F.; Renzoni, G. E.; Borden, W. T.; Michl, J., A Doubly Pyramidalized Olefin Matrix-Isolation Spectroscopy of Tricyclo 3.3.2.0(3,7) Dec-3(7)-Ene. Journal of the American Chemical Society 1986, 108, (12), 3544-3545. 167 Garbacia, S.; Desai, B.; Lavastre, O.; Kappe, C. O., Microwave-Assisted Ring-Closing Metathesis Revisited. On the Question of the Nonthermal Microwave Effect. Journal of Organic Chemistry 2003, 68, (23), 9136-9139. 168 Kappe, C. O., High-Speed Combinatorial Synthesis Utilizing Microwave Irradiation. Current Opinion in Chemical Biology 2002, 6, (3), 314-320. 169 Microwave-Assisted Combinatorial Chemistry. In Microwaves in Organic Synthesis, Ed. Loupy, A., Wiley: 2002; p 405-433. 170 Larhed, M.; Moberg, C.; Hallberg, A., Microwave-Accelerated Homogeneous Catalysis in Organic Chemistry. Accounts of Chemical Research 2002, 35, (9), 717-727. 171 Wathey, B.; Tierney, J.; Lidstrom, P.; Westman, J., The Impact of Microwave-Assisted Organic Chemistry on Drug Discovery. Drug Discovery Today 2002, 7, (6), 373-380. 172 Lidstrom, P.; Tierney, J.; Wathey, B.; Westman, J., Microwave Assisted Organic Synthesis a Review. Tetrahedron 2001, 57, (45), 9225-9283. 173 Melder, J. P.; Pinkos, R.; Fritz, H.; Prinzbach, H., The Pagodane Route to Dodecahedranes Dodecahedradienes Unusually Pyramidalized, Isolable Olefins. Angewandte Chemie-International Edition in English 1990, 29, (1), 95-99.

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173 174 Paquette, L. A.; Carr, R. V. C., Response of Syn-1,2,3,4,5,6,7,8-Octahydro-1,4 5,8-Dimethanonaphthalene and Related Molecules to Oxidation with Ozone, Singlet Oxygen, and Triplet Oxygen Strain and Steric Effects as Controllers of Reactivity. Journal of the American Chemical Society 1980, 102, (25), 7553-7559. 175 Baskerville, C., The Decomposition of Chloroform. the Journal of Industrial Engineering Chemistry 1912, 4, 281, 362. 176 Schulte, J. W.; Suttle, J. F.; Wilhelm, R., Chemical Effects Produced in Chloroform by Gamma-Rays. Journal of the American Chemical Society 1953, 75, (9), 2222-2227. 177 Schaap, A. P.; Faler, G. R., Mechanism of 1,2 Cycloaddition of Singlet Oxygen to Alkenes Trapping a Perepoxide Intermediate. Journal of the American Chemical Society 1973, 95, (10), 3381-3382. 178 Kwon, B. M.; Foote, C. S., Chemistry of Singlet Oxygen .50. Hydroperoxide Intermediates in the Photooxygenation of Ascorbic-Acid. Journal of the American Chemical Society 1988, 110, (19), 6582-6583. 179 Kwon, B. M.; Foote, C. S., Chemistry of Singlet Oxygen .53. Environmental-Effects on the Photooxygenation of 2-Methoxy-3-Methyl-2-Cyclopenten-1-One. Journal of Organic Chemistry 1989, 54, (16), 3878-3882.

PAGE 189

BIOGRAPHICAL SKETCH Zhai Yi-An was born in Xupu, Hunan Province, P. R. China. He received his B.S. in chemistry and M. S. in organic chemistry from Xiangtan University in July 1993 and Shanghai University in March 1996, respectively. After four years working in Shanghai Institute of Organic Chemistry in China, he came to the University of Florida as a research scholar in Dolbiers group. He became a graduate student of organic chemistry in Spring 2002 and joined Prof. William R. Dolbier, Jr.s lab. Yian Zhai will receive his Ph.D. in May 2005. 174


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THE CHEMISTRY OF 1,1,2,2,9,9,10,10-OCTAFLUORO[2.2]
PARACYCLOPHANES


















By

YIAN ZHAI


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA


2005
































Copyright 2005

by

Yian Zhai































The work presented in this dissertation is dedicated to my wife Lazhen.















ACKNOWLEDGMENTS

I would like to thank my advisor and the chair of my committee, Dr. William R.

Dolbier, Jr., for affording me the opportunity to study in his laboratory. The time spent

under his direction has been invaluable, and I am indebted to him for his patience,

guidance, and encouragement.

With as much owed respect and thanks, the friendship and mentoring of Dr. Merle A.

Battiste will not be forgotten as well as his insight and inspiration on my research.

Without Dr. Ion Ghiviriga's help in NMR characterizations, I would have had serious

problems in identifying compounds; I also thank Dr. Merle A. Battiste, Dr. Ion Ghiviriga,

Dr. Weihong Tan, and Dr. John Sabin for being on my committee and for their time and

effort. I acknowledge Dr. Khalil Abboud for the x-ray analysis with great appreciation.

Personally, I would also like to thank my wife La-Zhen Xiang. Without her love and

support, I would not be in this position today. I also thank my family: mother Feng-Xian

Zhang, father Jian-Ting Zhai, my sister Xiao-Chun Zhai, Xiao-Yan Zhai, my mother-in-

law Qin-Ju Tang, and father-in-law Li-Wang Xiang. Their support and love are

acknowledged, and I thank them for that.

Over the years I have been taught by some truly inspirational teachers, I extend my

thanks to Dr. Wei-Jue Ding for her mentoring and for opening the door into the realm of

organic chemistry. I wish to thank past and present members of the Dolbier group for

their friendship and help. I also want to take a moment to specifically thank Dr. Jian-Xin

Duan for his friendship and help in everything. I would also like to give specific thanks to









Dr. David Powell, and the MS group as well as the CHN group for their technical support

with my MS characterization elemental analysis. Dr. Kirk S. Schanze's group provided

the UV and fluorescence instruments for some of my compounds. Dr. Yao Liu helped me

in the fluorescence spectra characterization.

Finally, I appreciate everything that the Chemistry Department has done during my

time here.













TABLE OF CONTENTS
page


A C K N O W L E D G M E N T S ....................................................................... .....................iv

LIST OF TABLES .............. ................. ........... .............. ............ viii

LIST OF FIGURES ................................... ...... ... ................. .x

ABSTRACT .............. .................. .......... .............. xiv

CHAPTER

1 IN T R O D U C T IO N ........................................................................... .....................

1.1 A Brief History of Cyclophane Chemistry .......................... ....................1
1.1.1 [2.2] Paracyclophane..................... ..... ......................... 3
1.1.2 O their C yclophanes...................................................... ................ ..5
1.2 The Physical and Chemical Properties of Cyclophanes .............................10
1.3 1, 1, 2, 2, 9, 9, 10, 10-Octafluoro[2.2]paracyclophane (AF4) ...................14
1.4 Aryne Chem istry ................. ................. ......................... .. .....17

2 4,5-DEHYDRO- AND 4,5,15,16-BIS-
DEHYDROOCTAFLUORO[2.2]PARACYCLOPHANES: FACILE
GENERATION AND EXTRAORDINARY DIELS-ALDER REACTIVITY.......24

2.1 Introduction .................................................................. ................ ....... .... ........ 24
2.2 R results and D discussions ...................................................... ..... .......... 26
2.2.1 Synthesis of Aryne Precursors....................................................26
2.2.2 Reactions of 4, 5-Dehydrooctafluoro[2.2]paracyclophane, 1........27
2.2.3 Reactions of 4,5,15,16-Bis-
(Dehydro)octafluoro[2.2]paracyclophane, 17..............35
2.2.4 N M R D iscussion.100............. .................................. ............... 36
2.2.5 X -ray D discussion ................................................. ....... ........ 38
2 .3 C on clu sion ..............................................................4 0
2.4 E xperim mental .......................................... ................... .. ...... 4 1

3 CADOGAN METHOD AND REACTION MECHANISM ..................................55

3.1 Introduction ............. .. ... .. ............ ............... ................ 55
3.2 R results and D discussion ........................................ ........................... 56
3.2.1 The Cadogan M ethod.................................. ....................... 56
3.2.2 E ne R eactions...................... ................ .............. .............. 57









3.2.3 2-Methoxynaphthalene Reaction ....................................... 60
3.2.4 Tetracyclone R action ....................................... ............... 61
3.2.5 Norbornadiene Reactions............... ............................................. 62
3.2.6 Reaction with 1,3,5-Cycloheptatriene..........................................63
3.3 Mechanistic Study of AF4-yne .......... ................................................. 69
3.3.1 Base and Solvent Study .......................... ....................70
3.3.2 The Different Selectivity of the Two Methods..............................71
3.3.3 The Selectivity of AF4-yne Toward Diels-Alder and
E n e reaction .................... .................... .... ........... 74
3.3.4 t-Butoxide Ion A dduct ....................................... ............... 76
3.3.5 M mechanism ............. ...... .................... ........ .... .............. ..77
3.3.6 Isotopic Labeling Experim ents ...................................................82
3.3.7 Reactions in the Presence of Electron Trap Reagents ...................83
3 .4 C on clu sion ..............................................................8 5
3 .5 E x p erim en tal ........................................................................................... 8 7

4 EFFICIENT SYNTHESES OF NOVEL NAPHTHALENO- AND
ANTHRACENO-OCTAFLUORO[2.2]PARACYCLOPHANES.........................99

4 .1 Intro du action .............................................................. ................ 9 9
4.2 R results and D discussion ........................................ .......... ............... 103
4.3 U V and Fluorescence Spectrum ............................... ............................. 109
4 .4 C on clu sion .................................16.............................
4 .5 E xperim mental ............................... ..... .................... .... ........ ....... 117

5 N OVEL CAGE COM POUND ..................................................... ... .. .......... 121

5.1 Introduction ................................. ........................ .. ......... 121
5.2 R esult and D discussions ............................................. .......... ............... 124
5.2.1 Synthesis of Cage Com pound.................... .................. ................124
5.2.2 Cage w ith Triplet Oxygen................................. ............... 130
5.2.3 Cage with Chlorine ............. ............................... ............... 131
5.2.4 Cage with Singlet Oxygen ...................................... .......... 132
5.2.5 C age w ith B rom ine ........................................... ............... 134
5 .3 C o n c lu sio n ............................................................................................ 1 3 5
5.4 Experim mental .................. .......................... .... .... ................. 135
X -R A Y D A T A ........ .. .................................................................................. .... 14 2

L IST O F R E F E R E N C E S ............................................................................... ........... 158

BIOGRAPHICAL SKETCH .............. ................................................ 174














LIST OF TABLES


Table page

1-1 Structural features of AF4 and [2.2]paracyclophane11 ............................................15

2-1. Diels-Alder reactions from treatment of 4-iodooctafluoro[2.2]
paracyclophane, 1, with potassium t-butoxide. .................. ....................... 30

2-2. Diels-Alder reactions from treatment of 4, 15-diodo-octafluoro [2.2]paracyclophane,
18, with potassium t-butoxide, in refluxing solvent........................ .................36

3-1 [2+2+2] to [2+2] products ratio of norbornadiene with AF4-yne ............................63

3-2 Base and solvent effects in AF4-yne reaction with anthracene..............................70

3-3 B ase solubility in butyl ether solvent .............................................. ............... 71

3-4 Competition reactions of naphthalene to benzene............. .... .................72

3-5 Selectivity in Diels-Alder reaction under Cram conditions .............. ...............73

3-6 Competition reactions of benzene to 1-octene ................................. ............... 74

3-7 Competition reaction of anthracene with 1-octene in butyl ether for 5 hours
at 1 10 C under C ram condition ................................................................... ......74

3-8 Reaction of AF4-yne with olefins in butyl ether ......................................................75

3-9 The AF4-yne selectivity of DA over Ene reaction under Cadogan conditions
(3 h at 110C in butyl ether) .............................................................................. 75

3-10 Summary of t-butoxide adduct under Cram's conditions.................. ...............77

3-11 Ionization potential of alkenes26................................................................... .. ..78

3-12 IAF4 reduced to AF4 in refluxing butyl ethera ...................................................83

3-13 Additive effect on the reduction of AF4-yne with 1-octene under Cram conditions
at 110 C for 3 h ........................................................................84

3-14 Additive effect on the reaction of AF4-yne with anthracene under Cram conditions
at 1ll O C for 3 h ........................................................................85









4-1 Fluorescence spectra data of fluorinated [2.2]paracyclophanes.............................1 16

5-1 B ase screening results.......... .......................................... .............. .. .... ......... 126

5-2 Solvent effect in the reaction of pseudo-ortho-dilAF4 with anthracene
under m icrow ave conditions ............................................................................ 127














LIST OF FIGURES

Figure page

1-1 [2.2](1,3)Cyclophane............................................ .......... .......... .......... ...... 1

1-2 [2.2](1,4)Cyclophane.......................................... .. ........ ......... ............... 1

1-3 Chemical shift (1H NMR) and charge transfer complex of [2.2] paracyclophane ........3

1-4 Geometry of [2, 2] paracyclophane ......................................................................4

1-5 Different bridge connection of [2.2]cyclophane.......................................4

1-6 Chemical vapor deposition (CVD) polymerization.....................................5

1-7 7 Effect on arom atic protons ............................................................................ 6

1-8 Distances of two aromatic protons to the other benzene deck .............. ...............7

1-9 Synthesis of [2.2][1,4]naphthalenoparacyclophane..................................................7

1-10 Synthesis of [2.2](1,4)naphthalenophane................ .............. ...................... ..8

1-11 [2.2]Anthracenophane and [2.2](2,5)heterophanes ..........................................8

1-12 [2.2](1,4)A thracenophane......... ................. ................... .................. ............... 9

1-13 H highly condensed phanes ................................. ......... .................................10

1-14 Photo reaction of [2.2]naphthalenopahane...... ........... .....................12

1-15 Photo and thermal reversibility of [2.2](1,4)anthracenophane..............................13

1-16 Octafluoro[2.2]paracyclophane (AF4 ) ........................................ ............... 15

1-17 N itration and dinitration of AF4.................................................... ............... 16

1-18 G generation of benzofuran aryne ........................................... ......................... 17

1-19 C 14 L abelling experim ent................................................ ............................... 18

1-20 M ethods of benzyne generation .............. ...................... ............. ... ............ 18

1-2 1 A ryne w ith furan ............ .... .............................................. ............ ................. 19









1-22 Co-cyclisation of arynes with alkynes to phenanthrene derivatives .......................20

1-23 Palladium catalyzed reactions of allyl chlorides with benzyne.............................20

1-24 Palladium catalyzed reaction between allytributylstannane, allyl chloride, and
benzyne ..................................... ................................... ......... 21

1-25 Paracyclophane aryne .......................................................................... 22

1-26 [2.2]Paracyclophane bis-aryne ............................................................. ............... 22

2-1 Bis-paracyclophane aryne with furan reaction ...............................................25

2-2 M ono- and bis-A F4-yne ........................................... .................. ............... 26

2-4 D iels-A lder reaction of A F4-yne..................................................................... ...... 29

2-5 Products of 1,4-dimethylnaphthalene and 2,3-dimethylnaphthalene ........................31

2-6 Products of 2-methoxylnaphthalene with AF4-yne.................................................32

2-7 Products of furan and 2,5-diphenylfuran with AF4-yne.................. ....... .........33

2-8 Product of [2.2]paracyclophane with AF4-yne (bold shifts on this structure
indicate protons pointed toward the viewer) ......... ................... ................34

2-9 Products of bicyclo[2.2. 1]hepta-2,5-diene with AF4-yne .............................. 35

2-10 The bis-Diels-Alder reaction of AF4-yne..... .......... .................................... 37

2-11 ORTEP drawing of anthracene adduct 5 and endo furan adduct 12a......................39

2-12 ORTEP drawing of [2.2]paracyclophane adduct 14 and bis naphthalene
ad du ct 2 0 ............................................................................ 3 9

3-1 Decomposition of benzene-diazonium slat....................................... ............... 55

3-2 1-O ctene w ith A F4-yne reaction ...................................................................... ..... 57

3-3 Chemical shifts of cyclopentene and cyclohexene products ....................................58

3-4 Chemical shifts of products from the reaction of a-methylstyrene with AF4-yne...... 60

3-5 Retro Diels-Alder reaction of 2-methoxynaphthalene adduct to phenyl anthraceno[2.2]
paracyclophane .............. ................ .............. .... ........ ...... ...... 61

3-6 Chemical shifts of tetracyclone with AF4-yne product .....................................61

3-7 Chemical shifts of cycloheptatriene products 8 and 9 ...........................................65









3-8 Primary AF4-yne ene product with AF4-yne reaction to products 8a&8b .................68

3-9 SRN1 reduction of IAF4 to AF4 ......... ..... ............. ............ ............. ... ...........80

3-10 Reduction mechanism of IAF to AF4 in the presence of olefin ..............................81

3-11 Olefin with KOtBu complex ............. .. .............. .......... ...................... 82

4-1 Anthracenophane 1 and naphthalenophane 2................................. ...... ...............100

4-2 [2.2](1,4)(9,10)anthracenophane 3, [2.2] paracyclo(9,10) anthracenophane 4 and
[2.2](1,4)naphthaleno(9,10)anthracenophane ..................................................... 100

4-3 Polyfluoroaryl [2.2]cyclophanes 6 and 7.............................................. ............... 101

4-4 Diles-Alder reaction of mono and bis-AF4-yne....................................................... 102

4-5 Bridge fluorinated [2.2]cyclophane 12, 13, 14 and 15 ......................... ................. 103

4-6 Reaction of adduct with 3,6-dipyridinyl-1,2,4,5-tetrazine 16 .............................104

4-7 Fragm ent of [2.2]cyclophane 12........................................................... ............... 105

4-8 Chemical shifts of [2.2]cyclophane 12, 13, 14 and 15 ........................ ...............106

4-9 Dimerization of phenyl anthracenophane 21................................. .................. ....108

4-10 ORTEP drawing of compound 21 .............. ..... .......................................... 108

4-11 UV spectra of bridge fluorinated [2.2]cyclophanes 12-15 ...................................10

4-12 Fluorescence spectra of bridge fluorinated [2.2]cyclophane.................................111

4-13 UV spectra in dichloromethane of compound 21 and 22 compared to
com pound 12 and 13. ........... .......................... ........ ... .. .. ........ .. .. 113

4-14 Fluorescence spectra in dichloromethane of compound 21 and 22......................14

4-15 Fluoresence of Diels-Alder products in dichloromethane ....................................115

5-1 P yram idalized alkene........................................................................ ...................122

5-2 Som e pyram idalized alkenes ............................................. ............................ 123

5-3 Tribenzo-4,7-dihydroacepentalene derivative ...........................................................123

5-4 4,5,15,16-bis(dehydrooctafluoro[2.2]paracyclophane 4 and 4,5,12,13-
bis(dehydrooctafluoro[2.2]paracyclophane 5................. ............... ............... 124









5-5 The reaction of the pseudo-ortho-4,12-diiodooctafluoro[2.2]paracyclophane with
anthracene ............... .... ............. .......... .................. ......... 124

5-6 NMR assignments of pseudo-ortho-diiodoAF4 with anthracene products under
C ram conditions ...................... ...................... .. .. ............... ....... 125

5-7 ORTEP drawing of the cage compound (right) and epoxide (left) ...........................129

5-8 Tricycle[3.3.2.03'7]-dec-3(7)-ene 10 and dodecahedradiene 11 ............................130

5-9 Cage compound reaction with oxygen ........................................... ............... 130

5-10 Syn-sesquinorbornene ................ ......................... ...... ........ ... ............... 131

5-11 Bubbling oxygen through the solution of cage compound...............................132

5-12 Trapping the intermediate of the reaction of singlet oxygen with pyramidalized
alk en e .............................................................................13 3

5-13 Compound 14 and cage with singlet oxygen product 15.....................................134

5-14 Reaction of cage with bromine...................................................... ................. 135
















Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy

THE CHEMISTRY OF 1,1,2,2,9,9,10,10-OCTAFLUORO[2.2] PARACYCLOPHANES

By

Yi-An Zhai

May 2005

Chair: William R. Dolbier, Jr.
Major Department: Chemistry

The chemistry of [2.2]cyclophanes has a number of unique and interesting

theoretical and practical aspects that have attracted the interests of organic chemists for

more than 50 years. It has been demonstrated in earlier work from our lab that the

chemistry of 1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane differs significantly form

that of its non fluorinated analogs.

The initial research in the current project involved the discovery of two good

methods for the generation of 4,5-dehydro and 4,5,15,16- bis(dehydro)-1,1,2,2,9,9,10,10-

octafluoro[2.2]paracyclophane-yne (AF4-yne and bis-AF4-yne) chemistry. The AF4-yne

generated from the reaction of potassium t-butoxide with iodo AF4 derivatives gave very

high yields for Diels-Alder (DA) reactions, including the very poor DA substrate,

benzene. Bis-AF4-yne also gave high yields for DA reactions. A new synthetic method of

synthesizing new bridge fluorinated polynuclear paracyclophanes has been developed by









using these DA adducts as intermediates. The physical and chemical properties of those

new paracyclophanes were investigated.

When AF4 aryne is generated from the nitrosyl acetamide AF4 derivative, it has a

very different reactivity towards alkene substrates compared to that generated from IAF4

via the KOtBu method. Experiments including isotopic labelling reactions were carried

out to gain an understanding of the differences observed for the two methods.

A novel cage compound was discovered by the reaction of pseudo-ortho-diiodo-

AF4 with KOtBu and anthracene. The physical and chemical properties of this cage

compound were investigated.

Finally, a study of the reduction of AF4-yne to AF4 was carried out, and it was

found that electron acceptor reagents have an effect on the reduction rate of IAF4 to AF4.

This process might involve electron transfer (ET) to produce radical anion as reaction

intermediate.

The selectivity of AF4-yne toward DA reaction under different reaction conditions

was established, and it was found that the DA reaction of anthracene with AF4-yne is

2.7*104 times faster than the same reaction with benzene.













CHAPTER 1
INTRODUCTION

1.1 A Brief History of Cyclophane Chemistry

Cyclophane chemistry has been studied for more than one century and has been

broadened dramatically. Cyclophane chemistry has both theoretical and practical use and

plays an important role in the study of electronic interactions and system strain. It

demonstrates that two or more closely placed 7t electron clouds have both steric and

electronic interactions. Transannular interactions also play an important role in the

stabilization of the cations and anions generated from cyclophanes.

The first cyclophane was synthesized by Pellegrin1 in 1899 through Wurtz coupling

of 1,3-bis(bromomethyl)benzene (Figure 1-1).

CH2Br

2 Na
CH2Br


Figure 1-1 [2.2](1,3)Cyclophane

Brown and Farthing synthesized [2.2] paracyclophane in 1949 by pyrolysis of p-

xylene (Figure 1-2), and published a low resolution X-ray structure analysis.2'3 German

chemists Ltittringhaus4 and Huisgen5 first reported the synthesis of alphatic bridged

cyclophanes.






Figure 1-2 [2.2](1,4)Cyclophane









These studies illustrated that the aromatic rings in cylcophanes are not planar but

distorted out of planarity by bending. The x-ray study unequivocally revealed that a

benzene ring can be distorted into boat-, chair-, and twist-forms by clamping or bridging

them in cyclophanes. These aberrations led to unusual spectroscopic properties and

chemical reactivities.

The interaction in the [2.2]paracyclophane between the two benzene rings leads to a

novel extended 7t-electron system. The Highest Occupied Molecular Orbital (HOMO) is

higher than that of the corresponding alkyl benzene; the Lowest Unoccupied Molecular

Orbital (LUMO) is lower than that in the open chain molecule. Thus, the energy gap

between the HOMO/LUMO is much lower than the open chain compounds. The same

type of interaction, albeit weaker, exists in the [3.3]cyclophane but is absent in the more

widely separated [4.4]cyclophane, where the individual benzenes behave as separated 7t-

electron systems.

Cyclophane chemistry gives an opportunity to increase the distortion gradually and

successively, which changes the chemical and spectroscopic properties of the aromatic

units. Some interesting functionized units can be placed very close to the aromatic ring.

For example, one can compare the transannular electronic effects and steric strain of

multi-layered cyclophanes or heterocyclophanes with these in the parent hydrocarbon

compounds.6 Cyclophane chemistry also has found applications. Cyclophane may serve

as a building unit for nests, hollow cavities, 'multi-floor' structures, helices, macro-

polycyclics, macro-hollow tubes, novel ligand systems, etc. Cyclophane chemistry also

has importance in supermolecular chemistry, molecular recognition, and may be used as a

building block for organic catalysts (novel ligand) and crown ethers.6-8









How far can aromatic rings be distorted? What are the physical and chemical

properties of these cyclophanes? These questions have been pursued for decades. The

chemistry of uniquely strained [2.2]paracyclophane and other cyclophanes has been the

subject of research since Cram's first description of [2.2]paracyclophanes.9 Since then,

numerous publications have emerged. Many different cyclophanes such as meta, para and

heterocyclophanes have been synthesized and studied.

1.1.1 [2.2] Paracyclophane


The [2.2] paracyclophane is a special example and reflects the essence of

cyclophane chemistry. Its two aromatic rings are placed face to face and have a chair-

like configuration instead of planar (deformation of the benzene ring), due to the 7t-

electron interaction between the two aromatic rings. Chemists are also interested in the

transannular electronic effects on the chemical reactivities of the ring and bridge. Their

reactivity is induced by the other ring and also causes a charge transfer interaction

(Figure 1-3) between the two aromatic rings.8'10

16 15 6.37

1 1 305


5 4

Figure 1-3 Chemical shift (1H NMR) and charge transfer complex of [2.2]paracyclophane

In [2.2] paracyclophane, the aromatic proton signal appears at 6.37 ppm, shifted

about 0.5 ppm upfield from that of p-xylene.9 This is due to a shielding effect from the

ring current of the benzene ring on the opposite deck.

According to Cram,10 the stereochemical course of several polar addition and

substitution reactions at the bridge position of [2,2] paracyclophane system is best









explained on the basis of a species similar to 1. The cation positive charge can be

distributed over both aromatic rings to compensate for the bond angle strain.

Figure 1-4 shows the approximate structure based on the x-ray crystal structure.11

The intermolecular separation (d) between the central carbon atoms of the two benzene

rings is shortened to 3.09 A (the normal Van der Waals separation between parallel

benzene rings is set at 3.40 A as a minimum). The two benzene rings are in boat

configuration. This is attributed to a considerable transannular 7t-7t overlap. The bridge

bond length is unusually large, 1.630 A at 291 K (X-ray structure analysis was taken at

93 K) to compensate for the transannular steric and electronic repulsion.





Ic Id cl f



a. 126 c 2.7 e 1.394
P 11.2 d 3.09 f 1.569

Figure 1-4 Geometry of [2, 2] paracyclophane11

The bond angle and bond length deformations, as well as the face to face

compression of two benzene rings, lead to high ring strain in cyclophanes. Boyd

measured the heat of combustion of cyclophanes 2, 3, 4 (Figure 1-5), and determined

their strain as 12, 31, 23 kcal/mol, respectively.6' 12-14







2 3 4


Figure 1-5 Different bridge connection of [2.2]cyclophane









Chemical vapor deposition (CVD) polymerization of [2.2]paracyclophane (Figure

1-6),15 at 550"C and 0.5mm pressure can form a thin, tough, polymer film called

"parylene" on the objects with true confirmality of the coating to all surfaces including

deep penetration into small spaces. This film has been found to be useful at temperatures

up to 130C.16


heat, CVD H2C

LH2C \/


2n H2 H2
2nr --- C C
L 2n

Figure 1-6 Chemical vapor deposition (CVD) polymerization

1.1.2 Other Cyclophanes

Nonbenzenoid aromatic compounds, such as azulene, tropolone, etc, are also

important in aromatic chemistry. These compounds have interesting deformation

structures caused by bridging. The charge transfer effects and R-electron cloud

interactions can be examined by bringing two nonbenzenoid rings together. Cyclophanes

which contain tropylium ions have been synthesized to test the charge-transfer

interactions.17, 18 When the tropylium rings are placed in a face-to-face position (9)

(Figure 1-7), the tropylium protons move to higher fields in the NMR spectrum( A 61.22

ppm) than those unbridged tropylium ions (6=9.28 ppm). This high-field shift is

attributed to the diamagnetic ring current effect of the benzene ring and the enhanced

electron density due to a charge-transfer effect. The singlet protons of a benzene ring in

stair-like compounds 7and 8 are at much higher fields than those in compounds 5, 6 and










9(1 6 1.2 ppm). The benzene ring protons in 5 and 6 are nonequivalent because of their

fixed geometry (NMR time scale). The ring-flip of 8 does not occur until 120C, whereas

the equilibration in two conformers of 6 happens at a higher temperature.

8.76
8.93
HH H
8.49 H -

H ) 5.51 H
7.76 H
H00 7.63 H H
.00 7598 4.76


H 7.19 7.69 H H 7.31
7.71
5 6 7
H 8.84
7.43 H 7.7 oH- -Me
7.70H-- Me
H H 8.06


6.94 H -H5.70

7.20

8 9

Figure 1-7 7t Effect on aromatic protons

[2]Azuleno[2]phanes 10 and 12 (Figure 1-8) are 107 systems.19' 20 The C(9)-C(10)

bond (azulene numbering) is elongated, and the azulene ring and benzene ring in

compound 10 are distorted up to 90 and 13.80, respectively. The distance between the

single proton and the benzene rings in the intermediates for 10, 11, and 12 are estimated

to be 1.20, 1.50, and 1.75 A, respectively depending on the different barriers to ring

inversion, which stem from the extent of steric crowding in the intermediate between the

single proton and the neighboring benzene ring.




















11

Figure 1-8 Distances of two aromatic protons to the other benzene deck

The cylcophanes with naphthalene rings and anthracene rings are of special interest,

because naphthalene and anthracene have a more extensive aromatic core. It would be

interesting to study the nature and extent of deformation of the naphthalene ring and

anthracene ring, the strain energy, and static and dynamic stereochemistry, as well as

charge transfer effects between neighboring aromatic units.

Naphthalenophane 13 was first synthesized in low yield from [2, 2] paracyclo-

phane by the annulation method in 1963 (Figure 1-9).9 Then, Wasserman and Keehn

reported the synthesis by coupling the p-xylene in situ from the pyrolysis of quaternary

ammonium salt with silver oxide in 41% yield,21' 22 which is an anti- and syn- mixture


e Br -Br
Xylene \
reflux, 10h (Et)3P


Figure 1-9 Synthesis of [2.2][1,4]naphthalenoparacyclophane









that can be separated by crystallization. The optimum procedure to produce 13 would be

using the photochemical sulfur extrusion method with triethyl phosphate as a solvent.23

A considerable number of investigations have been made into the chemistry of

[2.2](1,4) naphthalenophanes. The syn- and anti- isomer 14 and 15 were first synthesized

by elimination-cycloaddition of 4-methyltrimethylammonium hydroxide in 3% yield

(Figure 1-10) each.24 The anti- configuration was confirmed by an alternate nine-step

synthesis, in which only anti- isomer was generated. Wasserman and Keehn modified the

procedure and got 40% anti- isomer and 4% syn- isomer.21 A highly efficient route to

compound 15 was designed by Brown and Sondheimer,25 which involved the solvolysis

of the corresponding ditosylate 16.

CH20Ts



CH20Ts
14 15 16

Figure 1-10 Synthesis of [2.2](1,4)naphthalenophane

Anthracenophanes are virtually 1,4- or 9,10-disubstituted anthracenes, which have

lower ionization potential than naphthalene or benzene. Golden first reported [2.2] (9,10)-

anthracenophane (17) (Figure 1-11) in 1961.26 The synthesis and electronic absorption

and emission spectra of five member ring incorporated anthracenophanes (18) were

reported in 1977.27 28





X=O, S
17 18


Figure 1-11 [2.2]Anthracenophane and [2.2](2,5)heterophanes









CO2Et CH2Br
1) LiAIH4
S 2) PBr3
CH3 CH3

CH2NMe3
1) NMe3 \OH
2) Ion exchange -
resin |
CH3







19

Figure 1-12 [2.2](1,4)Athracenophane

In order to study the effect of transannular 7t-electron interactions in excimer

fluorescence, photodimerization, and ESR phenomena, Misumi et al.29' 30 have

synthesized many cyclophanes which incorporate anthracenes. The first compound in this

series was synthesized from dimerization of 1,4-anthraquinodimethane, in turn derived by

a Hofmann elimination of a quaternary ammonium hydroxide (Figure 1-12). The anti-

isomer (19) was obtained in 14% yield.

Other cyclophanes, such as hetero- and meta-cyclophanes were also synthesized.31

Replacing benzene rings with pyridine rings results in [2.2](2,6)pyridinophane 20 (Figure

1-13).32 One of the pyrenophanes, [2.2](1,3) pyrenophane 21, was reported by Misumi at

al.,33 as well as a few "mixed," "asymmetrical" pyrenophanes. Porphyrine 22, which is

very important in biological transformations, also has cyclophane characteristics and is

considered a special cyclophane serial.29 Calixarenes 23 belong to the [ln]cyclphane









group; their basket-like shape was adapted to host-guest or receptor-substrate

chemistry.31







20 21

R



NH N / OHOH R
/ HO -
N HN -HO
S/ R


22 23 R

Figure 1-13 Highly condensed phanes

1.2 The Physical and Chemical Properties of Cyclophanes

Unusual structural features help chemists understand molecules and pursue their

structural distortion limit. The works in this field provide useful information in

developing, confirming, and refining the theoretical underpinnings of science.

Cyclophane chemistry has provided insight into the ways in which molecules distribute

strain, the effects of strain on molecular reactivity, transannular effects on chemical

stability and spectroscopic properties, and as well as the criteria for aromatic stabilization.

The X-ray analysis of [2.2](1,4)paracyclophane reveals that the two benzene

moieties are separated by a distance of 299 pm, which is much smaller than the usual xn-

system van der Waals contact distance of 340 pm between the two parallel aromatic rings

in crystals.34 As shown (Figure 1-4), the bridged carbons are only 278 pm apart, and the









center carbons are 309 pm, which means that the two aromatic rings are bent out of plane

by an angle of 12.6.

It is obvious that two 7n clouds pressed hard against each other should lead to

additional steric repulsion between the two rings. One would intuitively assume that this

steric repulsion would be relieved by lowering the number of interacting 7t-electrons. In

contrast, the bending does not unambiguously increase or decrease the 7t electron

ionization energies.35 The benzene system would be deformed and decrease its

aromaticity due to lack of planarity, thus, ionization should be facilitated. On the other

hand, bending a 7t-system would localize its bond, i.e., forms a more polyenic type of

structure which would increase the ionization energy.

Model calculations using localized orbitals have shown that out of plane

deformations of ethylene have a negligible influence on its 7-1 ionization energy, as long

as they do not exceed certain limits, typically about 20 for bending and/or twisting

modes.36'37 The deformation results in decreasing ionization energy if it is not

compensated by the necessary admixture of low-lying 2s atomic orbitals to accommodate

the bulge, which would increase the ionization energy.

The study of 7-electron energies in a series of cyclophanes by photoelectronic (PE)

spectra indicates that ionization energies of 7-electrons are affected by the substituent

group in the benzene deck.35 The mean ionization energy for the two HOMOs of methyl

substituted benzenes decreased by 0.5 eV. The cyclophanes had a smaller decrease in

ionization energy. The ionization energy of superphane is not close to 6 eV as expected,

but rather 7.5 eV. The monobromine substitution in the benzene ring has negligible

influence on the PE spectra, while the amino group shifted the PE band towards the lower









field. Bridge octafluoro paracyclophane (AF4) is an extreme example. The fluorine

substitution induced the ionization energy shifts up field from 1.0 to 1.3 eV for the

corresponding orbitals. The analysis of PE spectra leads to the recognition of a novel

consequence of the "fluoro-effect".

Cyclophanes involving higher aromatic systems have a lower ionization potential,

especially cyclophanes with incorporated anthracene. The syn- and anti-isomers of [2,

2](1,4)naphthalenophanes21 38, 39 (Figure 1-14) can be interconverted by light. Irradiation

of syn-isomer 25 in degassed benzene leads primarily to the anti-isomer 24, while

continued irradiation of the 24 solution gives other products. Irradiation with light above

hv 254 nm
[intermediate] ---190
Si_ -190oCI



26a / -h 4+4 27
2+2 I hv -hv





/ 200C



26 24

2+2 >1hv350nm 28

>1900C



-: ,25


29

Figure 1-14 Photo reaction of [2.2]naphthalenopahane









290 nm gives intermolecular rearrangement product 28, which rearomatizes to 24 at room

temperature with a half life time of 76 s at 20C. 28 is a kinetic product, because

extended irradiation for 10 days at room temperature leads to the thermodynamically

more stable product, dibenzoquinene 29, in 25-50% yield. This compound is confirmed

by x-ray, and presumably arises through two sequential [27n + 27n] additions (26a first then

26).

Normal naphthalene does not react with oxygen, but anti-[2.2]paracyclonaph-

thalene reacts with singlet oxygen to form transannular peroxide.22 This is due to the

deformation of the naphthalene ring by the strain.




30



2200C hv 374 nm
or hv 254 nm


/' 2400C




31 32

Figure 1-15 Photo and thermal reversibility of [2.2](1,4)anthracenophane

[2.2]Anthracenenophanes (Figure 1-15) are fascinating compounds. Both the anti-

and syn- isomers (31 and 32) are synthesized from the dimerization of 1,4-anthraquino-

dimethane.30,40 The syn-isomer 32 can be rearranged thermally to the anti structure 31.

When light is used, the isomer 32 undergoes a rapid photo induced cyclization reaction to

form cage compound 30, which is both thermally and photochemically reversible.









The transannular effect on the spectroscopy of cyclophanes has been utilized in the

chemical luminescence polymer. 7t-Conjugated polymers having cyclophane derivatives

as the key unit have been synthesized by Chujo et al.41 These polymers were soluble in

common organic solvents, and self standing thin films exhibit strong blue photophoto-

luminescence in solution and strong bluish-green photoluminescence in solid state.

1.3 1, 1, 2, 2, 9, 9, 10, 10-Octafluoro[2.2]paracyclophane (AF4)

Fluorine has the largest electronegativity, while its Van der Waals radius is just

10% larger than that of hydrogen. The replacement of hydrogen by fluorine does not

cause much steric problem, but changes the bond dipolemoment dramatically. The C-F

bond, which is the strongest among the carbon-halogen bonds, is the shortest next to the

C-H bond but it is much stronger in energy. Accordingly, various types of

perfluorocarbons are both thermally and chemically stable compounds in sharp contrast

to perchlorocarbons. The electron cloud in the C-F bond is slightly polarized towards the

fluorine atom, thus electron repulsion between unshared electron pairs of fluorine atoms

is substantial. The characteristic features correspond to the stability of perfluorocarbons

against biological, chemical and physical stimuli.42 Perfluorocarbons have some salient

physical properties, such as low boiling point, insolubility in water and hydrocarbons,

and low surface tension.

Bridge fluorinated cyclophane (AF4), as mentioned above, has some unique

properties including its thermal and chemical stability. The synthesis of AF4 was a

challenge in organic chemistry for almost half of a century. The first chemical synthesis

of AF4 was published by Cram et al. in 1951,14 in which a highly diluted system was

used, and the reaction could not be scaled up. There are abundant derivatives of [2.2]

paracyclophane and other cyclophanes, but the derivatives of AF4 are scarce. One reason









for this is because of the lack of a large scale synthetic method for AF4. AF4 was

commercially unavailable until Dolbier's group solved this problem in 2000.43-47 The

interest in synthesizing AF4 is mainly driven by the industrial application of this

compound as a monomer for chemical vapor deposition (CVD) (Figure 1-6)

polymerization of AF4, known in industry as "parylene-HT". The C-F bond is not readily

oxidized, and compounds with multiple C-F bonds exhibit greatly improved oxidative

and thermal stability. The parylene-HT polymer has a much lower dielectric constant

(2.25) and a higher thermal stability (0.3% weight loss/h at 450"C) as well as a lower

moisture absorption,48 compared to the parent non fluorinated "parylene" polymer.

"Parylene-HT" film is expected to be an excellent insulator in Information Technology

(IT) industry.

F
F

F F

F F7 \

F F

Figure 1-16 Octafluoro[2.2]paracyclophane (AF4)

Table 1-1 Structural features of AF4 and [2.2]paracyclophane11
AF4 [2,2]
Paracyclcophane
a(deg) 11.8 12.6
P(deg) 12.6 11.2
c (A) 2.80 2.78
d (A) 3.09 3.09
e (A) 1.380 1.394
f (A) 1.577 1.569


The structure of AF4 11 is very similar to that of [2.2] paracyclophane.2 Some key

structural data are listed in Table 1-1 (also see Figure 1-16).









After successfully solving the problem of the synthesis of AF4, Dolbier's group

published several electrophilic substitution reactions of AF4. Nitration and dinitration of

AF4 (Figure 1-17) gave nitrated AF4 derivatives, which were reduced to amino-

compounds. Other functionalities can be introduced into the AF4 molecule by the

Sandmeyer reaction or coupling reaction, which opened the way to AF4 derivatives22 and

fluorinated cyclophanes.49-52

F F F F
F F F
Fuming HNO3 NO2



F F
F F98


F F F F
02N
F F N02BF4 F F F
F \ -F Supholane F F
F F 800C F NO2 F
33 34

pseudo-para:pseudo-meta:pseudo-ortho
= 1:1:1

Figure 1-17 Nitration and dinitration of AF4

Because fluorine is the strongest electron-withdrawing element, the bridge fully

fluorinated compound 1,1,2,2,9,9,10,1 0-octafluoro [2.2](1,4)paracyclophane (AF4) has

different physical and chemical properties than the non-fluorinated parent compound.

The effect of the neighboring aromatic ring electron cloud towards the reactivity of the

other ring is also an intriguing issue. For example, unsubstituted [2.2] paracyclophane has

a single 1H-NMR absorption for the aromatic proton at 6= 6.3 ppm, while this peak in

AF4 is shifted to 6= 7.3 ppm. When unsubstituted paracyclophane is treated with

bromine and iron, mono- or di-brominated [2.2] paracyclophane is the product,









depending on the mole ratio of bromine.24 There is no product under the same or harsher

conditions in case of bridge fluorinated AF4.51 When [2.2]paracyclophane was treated

with fuming nitric acid in glacial acetic acid, a mixture of dinitro[2.2]paracyclophane was

produced immediately.53 In contrast, the corresponding dinitro-AF4 can only be realized

by using a very strong nitration reagent, nitronium tertafluoroborate, in polar solvent

sulfolane and heated to 80C overnight.50 Fluorine substitutes deactivate the electrophilic

substitution reactions of AF4 dramatically. On the other hand, the same electron

withdrawing effect would make the aromatic protons more acidic in AF4 than that in the

non-fluorinated parent compound, and making it easier to deprotonate from the

fluorinated AF4.

1.4 Aryne Chemistry

The existence of aryne was first reported by Stoermer and Kahlert in the Chemical

Institute of University of Rostock over one century ago. 3-Bromobenzofuran was treated

with base in ethanol, and 2-ethoxybenzofuran was the product, 2,3-dehydrobenzo-furan

35 (Figure 1-18) was postulated as the reactive intermediate.54 Wittig and coworkers

proved the existence of ortho-benzyne later in 1942.55

Br
\- Base, ethanol
S\\ OCH2CH3


35

Figure 1-18 Generation of benzofuran aryne

It was a milestone in benzyne chemistry that Roberts et al. found solid evidence of

benzyne 36 in 1953.56 1-C13 Labeled benzene chloride was treated with potassium amide,









and a 1:1 ratio products 1- and 2- aniline were isolated (Figure 1-19). Since then, aryne

chemistry has been extensively studied and used in organic synthesis.

CI NH2
S -KNH2 N + C NH2
-KCl, NH3
36

Figure 1-19 C14 Labelling experiment

The triple bond in the intermediate is significantly weaker than the unstrained triple

bond. Intermediate 36 is better described as a strained alkyne rather than a biradical

because of its large energy gap between the singlet and triplet states of the biradical

(37.50.3 kcalmol-1).57 The formation enthalphy of the strained alkyne was 106.6 3.0

kcalmol-1 by Wenthold and Squires.57' 58 The corresponding bond length found

experimentally was 1242 ppm which is close to triple bond length 120.3 ppm and its IR

stretching absorption was 1846cm-1.59 Therefore, benzyne has alkyne-like reactivity. For

example, the Diels-Alder reaction, [2+2] reactions, etc. The methods of benzyne

generation as summarized in Figure 1-20.

X X N N

SN
/N: NH2

/ 36 COCO2H
r X 6 2 Co362H
Y N2+ NH2

Figure 1-20 Methods of benzyne generation

Benzene halide compounds were treated with a strong base such as an amide,60 to

remove the ortho-proton and generate benzyne via an anion. Dihalogen substituted

benzenes 61 were treated with lithium or magnesium to give the corresponding ortho-









metal halogen benzene, followed by Elb like elimination to form the desired benzyne.

Decomposition of benzenediazonium-2-carboxylate 62 is considered the best method of

benzyne generation and generally used in organic synthesis. Deprotonation of 1-amino-

benzotriazole derivatives by oxydation followed by extrusion of nitrogen to generate

benzyne.63 64

The fluoride ion displacement of the trimethylsilyl group by utilizing the large Si-F

bond energy gives a convenient route to benzyne under mild conditions (Figure 1-21). 65

I O SiMe3 Bu4NF F

LOTf 61%


Figure 1-21 Aryne with furan

The use of aryne in organic synthesis was well reviewed by Pellissier.66 The

reaction of arynes with lithioacetonitriles derivatives was important in the synthesis of the

basic skeleton of ergot and alkaloids.67'68 Aminoisoquinolines were synthesized through

aryne with two equivalents of 2-pyrridinylacetonitrile.69 Heteroarynes can be generated in

a similar manner and used in the synthesis of heterocyclic compounds.70

When transition metals are present, metal-aryne complexes can be formed. The

synthetic applications of metal-aryne complexes are limited due to the lack of a general

and mild method for aryne generation. Recently, Castedo and Yamamoto have reported

some examples of successful generation of metal-aryne complexes under mild conditions.

Palladium catalyzed co-cyclisation of aryne with alkyne produced the phenanthrene

derivatives exclusively in 63% yield (Figure 1-22).71 Pena et al. also described the

synthesis of phenanthrenes and naphthalenes by co-cyclization of arynes with alkynes.72'

73 In their later work, electron deficient alkynes, such as hexafluoro-2-butyne and









dimethyl acetylenedicarboxylate (DMAD) gave phenanthrene derivatives in the presence

of Pd(Ph3P)4, while with Pd2(dba)3, naphthalene derivatives were separated in high yield.

Finally, the intermolecular cycloaddition of arynes with DMAD can be made highly

chemoselective and be easily switched between the formation of phenanthrenes and

naphthalenes by appropriate catalyst selection. In addition, by the appropriate choice of

catalyst, the reaction can be selectively directed either towards the co-cyclisation of one

aryne molecule with two molecules of alkyne or to the reaction of two molecules of aryne

with one alkyne molecule.74' 75

R,
TMS Pd(OAc)2 R2
OTf P(o-tol)3, CsF 1


Figure 1-22 Co-cyclisation of arynes with alkynes to phenanthrene derivatives

R
-- TMS Cl Pd(5%) R

0 OTf CsF


R=H: 70% (100:0)
R=Me: 70% (70:30)
R=ph: 71% (73:23)

Figure 1-23 Palladium catalyzed reactions of allyl chlorides with benzyne

Yamamoto successfully used aryne as a highly reactive carbopalladation partner

with allyl chloride to give phenanthrene derivatives in high yields (Figure 1-23).76 In the

same way, benzyne also successfully co-cyclized with alkyne-alkene.

Aryne reacted with bis-xt-allyl palladium complexes in an amphiphilic fashion to

produce 1,2-diallyl benzene in high yields.77 The reaction of an aryne precursor with









allytributylstannane and allyl chloride in acetonitrile in the presence of 2.5 mol%

Pd2(dba)3 at 40C produces the corresponding diallyl benzene in 76% yield (Figure 1-24).

The reaction mechanism is the insertion of Pd(0) to allyl chloride to form the t-allyl

palladium complex 37, which is converted to bis-7t-allyl palladium complexes 38 via the

reaction with allyltributylstannane. The addition of two allyl groups of 38 to the benzyne

triple bond leads to the final products.

r` ^TMS +SnBu3 + /Cl Pd2(dba)3 2.5%
X OTf CH3CN, CsF

76%


(-Pd- ((-Pd-)) -Pd-

37 38


Figure 1-24 Palladium catalyzed reaction between allytributylstannane, allyl chloride,
and benzyne

The first 4,5-dehydro[2.2]paracyclophane aryne (Figure 1-25), reported by Cram in

1969, was generated from 4-bromo[2.2]paracyclophane 39 and gave three products.24

The total yield of cyclophane aryne intermediates is less than 30%. The dibromide

derivatives (40 and 41) show the same reactivity as monobromide to produce

intermediate 42. Bis-aryne cannot be generated from dibromide derivatives.


Br Br BrY Br4


40 41










SBr (CH3)3COK /\~ n 13)
(CH3)2SO +

4%
OH OH

SCH3

14% 10%

Figure 1-25 Paracyclophane aryne

Bis-dehydro[2.2]paracyclophane7 was generated from 4,5,15,16-tetrabromo[2.2]-

paracyclophane (Figure 1-26) by Cram.

Br
B n-BuLi, Et20

Br Br -78
Br 84%

Figure 1-26 [2.2]Paracyclophane bis-aryne

The perfluorinated o-benzyne had been isolated in cryogenic matrices by photolysis

of the corresponding phthalic anhydride,78'79 and the CASSCF calculation showed that

the singlet-triplet energy gap of tetrafluoro-o-benzyne was larger than that of non-

fluorinated benzyne by several kilocalories per mole.79 Radziszewski et al.80 identified

the C C bond stetching vibration of tetrafluoro-o-benzyne at 1878cm-1, while the length

of that is similar to C C bond. The chemistry of fluorinated benzyne differs

significantly from that of none fluorinated one, the former is much more electrophilic and

reactive. For example, tetrafluoro-o-benzyne reacted readily with thiophene.81' 82









Other benzynes, such as meta-, para-benzynes and heteroarynes, were also studied

extensively and summarized in an excellent review article by Wenk et al.83

Benzyne chemistry has been studied for over one century and is still a very active

research field. Exploring different aryne generation methods will bring new features into

aryne chemistry and help us understand more about its chemical reactivity. Bridge

fluorinated paracyclophane has just become commercially available recently, and

studying the AF4 derivatives would be cheaper than it was before. AF4 derivatives will

also bring new feature into cyclophane chemistry and reveal more electronic effects in

cyclophane chemistry. These derivatives may also service as new synthon for other

fluorinated cyclophanes.













CHAPTER 2
4,5-DEHYDRO- AND 4,5,15,16-BIS-
DEHYDROOCTAFLUORO[2.2]PARACYCLOPHANES: FACILE GENERATION
AND EXTRAORDINARY DIELS-ALDER REACTIVITY

2.1 Introduction

Benzyne was first discovered over a century ago by Stoermer and Kahlert,54 while

the landmark in benzyne chemistry is the isotopic labeling studies on the KNH2 mediated

reaction of chlorobenzene, which left little doubt on the existence of benzyne as a highly

reactive intermediate.56 The most striking feature of these dehydroaromatic intermediates

is their dienophilic reactivity with other aromatic systems as diene partners. Depending

on mode of generation and the nature of the aryne component, however, the yields in

these Diels-Alder type reactions can often be modest or poor.60 For example, 75% is the

best yield reported for benzyne addition to anthracene, considered one of the most

reactive aromatic substrates in Diels-Alder reactions with arynes.84' 85 In that case, the

benzyne was generated from benzenediazonium carboxylate, which is generally

considered to be among the best methods for carrying out Diels-Alder chemistry

involving benzyne.86 Benzene is a much poorer Diels-Alder substrate, and it yielded only

9% Diels-Alder adduct in a similar reaction with benzyne,87'88 although its reactions with

tetrafluorobenzyne and tetrachlorobenzyne (among the more reactive arynes) yielded 33

and 62% of adduct, respectively.89'90

Examples of 4,5-dehydro-[2.2]paracyclophanes in the literature are rare. The parent

4,5-Dehydro[2.2]paracyclophane appears to have been mentioned but once, in 1969 when

Longone and Chipman reported its generation by potassium t-butoxide promoted









dehydrobromination of 4-bromo-[2.2]paracyclophane in t-butylbenzene in the presence

of excess anthracene, with only a 15% yield of Diels Alder adduct being obtained.24'91

Their yield is similar to that obtained in Cadogan's original report of the use of this

method to generate benzyne from bromoaromatics, in which he obtained high yields of t-

butyl aryl ethers, but, when generated in the presence of anthracene only produced 21%

yield of tripticene.92

Although the Longone and Cram papers are the only mentions of dehydro[2.2]

paracyclophanes in the literature, there also exists another report by Cram in 1969 of a

bis-dehydro[2.2]paracyclophane,7 where sequential aryne-furan Diels-Alder reactions of

the nominal 4,5,15,16-bis-dehydro[2.2]-paracyclophane was carried out via the double

dehalogenation of 4,5,15,16-tetrabromo[2.2]paracyclophane (Figure 2-1).

Br
/Br n-BuLi, Et20 0
Br [\,/O
Br -78 C OC

O 84%

Figure 2-1 Bis-paracyclophane aryne with furan reaction

Because of competitive trapping by the nucleophilic t-butoxide, the use of

Cadogan's t-butoxide method to generate arynes has almost never been used to initiate

Diels-Alder chemistry. Following the successfully solving the AF4 synthetic issue, we

applied these conditions for dehydroiodination 4-iodo-1,1,2,2,9,9,10,10-octafluoro[2.2]

paracyclophane 2 to mono-AF4-yne 1, 49, 52 and the sequential double dehydroiodination

of 4,15-diiodo-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane 18 to bis-AF4-yne 1750

(Figure 2-2) which led to efficient Diels-Alder trapping of the intermediate arynes with

virtually no observed competitive interception of the intermediates by the t-butoxide ion.














1 17


Figure 2-2 Mono- and bis-AF4-yne

2.2 Results and Discussions

2.2.1 Synthesis of Aryne Precursors

The 4-iodo- and 4,15-diiodooctafluoro[2.2]paracyclophane precursors were

prepared from 1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane (AF4) by improved

procedures based on those previously published (Figure 2-3).51, 52 Noteworthy is the

double-nitration procedure, in which essentially equal amounts of the pseudo-ortho (4,12-

dinitro-), pseudo-meta (4,15-dinitro-), and pseudo-para (4,16-dinitrooctafluoro[2.2]

paracyclophane) products (23a, b, and c, respectively) are formed. The pseudo-meta and

pseudo-para isomers are readily separated from the pseudo-ortho isomer by column

chromatography, and it is this mixture of 4,15- and 4,16-dinitro isomers (23a and 23b,

respectively) that is used in subsequent steps to eventually synthesize a mixture of 4,15-

and 4,16-diiodooctafluoro-[2.2]paracyclophanes (18a and 18b, respectively). Since both

of these isomers lead to the same bis-aryne (17), this mixture was used as the "precursor"

of 4,5,15,16-bis-dehydrooctafluoro[2.2]paracyclophane. The reduction of nitro

compound by palladium (10%) on carbon with hydrogen at room temperature gives

quantitatively yield. Product was filtered through a short pad of silicon Gel to get rid of

palladium and carbon, while no further purification is necessary. Chromatography

purification was required for other reduction methods and the yield was much lower.











90% HNO3 Pd/C, Methanol, H2
F, F F F F
F -F F F F4 F
NO2 NH2
F_ F
a) 0C, NaNO2, H2SO4 F / F
HOAc
b), KI/H20, RT, 8h F / \ .F
F F


F F
F- --F FF X F
NO2+BF4- F \ F
F', / \ .F o5 equiv, sulfolane F. / \ F
F F 800C F F
X
25a, pseudo meta 1 4
25, X=N02 25b, pseudo para 49%
25c, pseudo ortho, 23%
Pd/C, Methanol
25a&b 26a&b (X=NH2)
H2
a) 0C, NaNO2, H2S04
HOAc, H20 2
26a&b HOAc, 2 pseudo meta, 18a 1
b)/H RT,8h pseudo para, 18b (X=I) 68%
b) KI/H20, RT, 8h
Figure 2-3 Synthesis of precursor

2.2.2 Reactions of 4, 5-Dehydrooctafluoro[2.2]paracyclophane, 1

When monoiodide 2 was treated with potassium t-butoxide in refluxing benzene, in

refluxing t-butylbenzene in the presence of stoichiometric amounts of naphthalene or

anthracene, the corresponding Diels-Alder adducts were obtained (Table 2-1), yields are

from 60% to 88% (Figure 2-4). The yields obtained with benzene and naphthalene are the

largest yet reported for aryne reactions with these substrates.

The structural integrity of compounds 3-5, as well as the stereochemistry of

compound 4, were demonstrated by NMR as illustrated below for the representative

adduct 5. In the proton spectrum of 5, the signals at 6.96, 7.32 and 7.27 ppm are the









second order multiplets that are characteristic for an ortho-phenylene group. The proton

at 7.65 has an extra coupling, most likely a through-space coupling with fluorine. Of the

three remaining aromatic CH's the two with protons at 7.20 and 5.84 are on the same

aromatic ring as revealed by their mutual 1H-13C long-range couplings. The final

aromatic proton, at 6.72, displays a nOe with the proton at 7.20, leaving the signal at 5.84

to be assigned as those facing the moiety originating from anthracene, and indeed the

signal at 5.84 displays nOe's with the protons at 7.27 and 7.65, and no nOe's with those

at 7.32 and 6.96. In a similar fashion, in compound 4, the proton at 5.78 ppm, displays

nOe's with those at 7.27 and 7.59, and no nOe with the alkene proton at 6.93, proof for

the endo stereochemistry. The upfield chemical shift of 5.78, which is comparable with

the 5.84 signal in compound 5 and significantly smaller than the 7.16 signal of the parent

cyclophane, is diagnostic for its position above the plane of an aromatic ring. The

chemical shift of the corresponding proton in compound 3, 6.91 ppm, demonstrates that

significantly less shielding is to be expected for a proton having a similar position above

a double bond.

Interestingly, no products deriving from nucleophilic capture of the presumed aryne

intermediates by the excess t-butoxide base were detected in any of these reactions, even

when the reaction was carried out in refluxing t-butylbenzene with no substrate added. In

this case a surprisingly high (78%) yield of the DA adduct (6) with t-butylbenzene was

obtained. This is in contrast to Longone and Chipman's results,91 as well as those of

Cram and co-workers,24 where t-butoxide adducts were found to be a major side product

in each of their respective studies where this method of aryne generation was used.















benzene

t-BuOK, reflux


548
141 8
6 78


naphthalene

t-BuOK
t-butylbenzene, reflux


F F
F\/F 727
7222
1258
128 8~ 1253
1340 1276F 759
578 F
F F 670 7 143 3
1187\ 127 3 476
1198
128 5 1452
F 1 141 1
F 693
4


(86%)


(86%)


(84%)


anthracene

t-BuOK
t-butylbenzene, reflux


t-BuOK
t-butylbenzene, reflux


(78%)


Figure 2-4 Diels-Alder reaction of AF4-yne









Table 2-1. Diels-Alder reactions from treatment of 4-iodooctafluoro[2.2]paracyclophane,
1, with potassium t-butoxide.
Substrate Solvent T(C) Time Product
(min) (%)
benzene benzene reflux (80) 20 3 (86)
naphthalene butyl ether reflux (142) 20 4 (88)
anthracene t-butylbenzene reflux (169) 15 5 (84)
t-butylbenzene t-butylbenzene reflux (169) 40 6 (78)
1,4- butyl ether reflux (142) 30 7(60)
dimethylnaphthalene (4.55:1/endo:exo)
2,3- butyl ether reflux (142) 30 8(67)
dimethylnaphthalene
2- butyl ether reflux (142) 30 9:10:11(18:4:27)
methoxylnaphthalene
furan t-butylbenzene reflux (142) 20 12a & b (80)
2,5-diphenylfuran butyl ether Reflux 30 13(84)
(142)
[2.2]paracyclophane t-butylbenzene reflux (169) 20 14 (86)
bicyclo[2.2.1]hepta- butyl ether reflux (142) 30 15 & 16 (67)
2,5-diene

The stereoselectivity exhibited by 1 in its virtually exclusive formation of the endo-

isomer (4) from naphthalene addition is remarkable, particularly since both molecular

mechanics and AM1 calculations predict only a very slight thermodynamic preference for

this isomer (0.75 and 0.02 kcal/mol, respectively).49 The endo transition state may be

favored because of a stabilizing 'herringbone' H-7n interaction93 of the 5.78 ppm protons

that interact with the 7t cloud of the endo benzene ring. This hypothesis were further

supported by AF4-yne reactions with 1,4-Dimethylnaphthalene and 2,3-dimethyl-

naphthalene. In 1,4-Dimethylnaphthalene reaction (Figure 2-5), product 7a&b were










obtained in 60% yield, in which aryne added exclusively to the ring without methyl

substitutes due to the steric effects. It is interesting that the product ratio of endo- and

exo- is about 100:37 with the more bulky aromatic ring inside. When 2,3-dimethyl-

naphthalene was the substrate, as expected, adduct 8 was produced in 67% yield, which

has a better electronic match with the electron deficient dieneophile, AF4-yne.

F, ,F


6.79
141.5


6.54
126.5


7.18
125.7

S7.47
124.7


8

Figure 2-5 Products of 1,4-dimethylnaphthalene and 2,3-dimethylnaphthalene

The reaction of AF4-yne with 2-methoxynaphthalene gave three products 9, 10, and

11(Figure 2-6) which comply with the electronic requirement: the addition occurred

mostly on the electron rich aromatic ring (totally 45% yields). The enol ether 9 was










hydrolyzed to give ketone product 11(27%). Only 4% adducts 10 occurred on the other

aromatic ring.

F2CF2 C CF2
F2C F2C
I CF2 / FCF F

F2C F2C

OCH3 O
9 11
CF2

F2C 0


C
F2
10

Figure 2-6 Products of 2-methoxylnaphthalene with AF4-yne

Furan has generally been considered to be a good Diels-Alder diene substrate in

trapping reactions with arynes. Indeed, when iodide 2 was treated with potassium t-

butoxide in refluxing t-butylbenzene in the presence of 1.1 equivalents of furan, an

almost 50:50 mixture of the endo- and exo-adducts 12 a&b of furan to aryne 1 was

obtained in 80% yield. The two isomers were distinguished by NMR videe infra), but a

corroborative X-ray crystal structure of the endo-adduct was also obtained. Interestingly,

in case of 2,5-diphenylfuran reaction with AF4-yne, the exo- and endo- ratio of two

products 13a:13b is 76:24 with exo-product predominant (Figure 2-7).










F F F F
7.22
7.41 129.2
128.8
134. 128.5 F F 7.29 134 29.7
F F 6.576 140.6 F F6.65
F--- F 6.51 / F127.1 /
118.7 127.7 81.4 118. 81.0
9, 5.88 1 5.91
119.3-Z- 119.
127.9147.5 O 127.3 150.4 144.1
F F F F 6.99
12a 12b

S F F F


128.3
130.2
135.0 7.33 F FO F F
F F F
118.6 6.64
127.
119.1 127.7 152.6 94.7 148.3

F "F 135.0 7.25 F F
127.2
7.85
128.3
na 7.56
7.50

13a 13b

Figure 2-7 Products of furan and 2,5-diphenylfuran with AF4-yne

There have been few previous reports in the literature of aryne additions to a [2.2]

paracyclophane. Perhaps the best example is Heaney's study of tetrafluorobenzyne,

where he got a yield of 44% of its addition to [2.2]paracyclophane in 1969.94 Such a

reaction also posed no problem for aryne 1, which, under the usual conditions, underwent

Diels-Alder addition to the hydrocarbon [2.2]paracyclophane in 84% yield (Figure 2-8).

Although fully characterized by NMR videe infra), an X-ray crystal structure of adduct 14

was also obtained. The regiochemistry of addition observed in the formation of adduct 14

was consistent with that reported earlier for the tetrafluorobenzyne/[2.2]paracyclophane

adduct.















11 8. 7 6 142. 0 39. b
FF 6. 47 126. 13 /.
125. 146. 133. O 128. 1
6.7 7. 07 6.95

126.4 147. 0 128.1 6.93
119.9 F 51. 133. 0
F 4.48 137.9 139.9
147. 5 5. 63
34. 2 33.3
2.38 2. 57
2.20 2. 98
14

Figure 2-8 Product of [2.2]paracyclophane with AF4-yne (bold shifts on this structure
indicate protons pointed toward the viewer)

Bicyclo[2.2.1]hepta-2,5-diene (norbomadiene) may act as diene or dienophile

depending on the reaction conditions and substrates. Stereochemistry of norbornadiene in

the DA reaction has been extensively studied,95-97 and there have been a few studies of

benzyne additions to norbomadiene. Both [2+2] and [2+2+2] addition products were

obtained for the reactions of tetrafluoro- and tetrachloro-benzyne with norbomadiene,

with ratios of 6:1 and 3:1, being observed respectively.98 The ratio of [2+2] and [2+2+2]

products did not change with the pressure of the reaction of tetrachlorobenzyne, which

was generated from butyllithium with hexachlorobenzene, with norbomadiene.99 The

reaction of AF4-yne with bicyclo[2.2.1]hepta-2,5-diene was examined to determine its

preferred selectivity. Four products (Figure 2-9), exo- and endo-[2+2+2]- addition

products 15 a&b, endo- and exo-[2+2]- addition products 16 a&b were obtained in a total

yield of 67.6% in butyl ether. The ratios of products 15a:15b:16a:16b is 62:27:3:8, with

[2+2+2] products being predominant. When reaction was carried out in neat

norbomadiene, the ratios of products changed to 74:12:10:4. This observed preference for

[2+2+2] products contrast with the regioselectivity of other arynes with norbornadiene. In











addition, all the major products are formed from the endo-addition to norbomadiene. The

endo selectivity for both types of products should be noted.

F F F F
.27 135. 1 119. 1 7.40 134. 5 118.8

14 128 7. 02 F L78
628.3F F 128.8 19.9
F F6 80 ~ 1.81 F F6. 6504
128. 3 33. 7 127. 8 2. 04

119. 9 127. 9 149. 9 23.8 145.3 31.
F F 47.0 / -l 88 F F 49.0 1. 66
3.37 3.40
21.3 56.4
1. 12 1.88
15a 15b


F F F F
7.56 1349 118.9 7. 23 134.8 18.4
128. 6 1. 92 129. 8
1.81
6.98 F --F 4278 7 31 F- -F
F F6. 62 128. 9 F F6. 92 124.6 46.6
131.1 128. 46. 6

1186 126. 7 142.7 118. 4 128. 5 147.9 2.86
F 50.4 40.3 F 137.1
136.9 0. 73
6.28 41.4
1. 21

16a 16b


Figure 2-9 Products of bicyclo[2.2.1 ]hepta-2,5-diene with AF4-yne

No adducts were able to be observed with other alkenes under these conditions,

neither [2+2] or Ene reaction being seen. Reactions with 1-octene, cyclohexene, t-

butylethylene and 1,3,5-cycloheptatriene were all attempted with neither [2+2] or ene

reaction being observed. instead, the AF4-I was observed to convert largely to AF4.

Mechanistic ramification of this adduct will be discussed further in next chapter.

2.2.3 Reactions of 4,5,15,16-Bis-(Dehydro)octafluoro[2.2]paracyclophane, 17

Incredibly, the yields of bis-adducts obtained from the sequential bis-dehydro-

iodination of diiodide 18a and 18b under analogous conditions were comparable to those









for the mono-adducts! Adducts 19-22 (Figure 2-10) were thus obtained in 83, 86, 80 and

84 % yields, respectively. Reaction conditions and results were listed in Table 2-2. All

adducts were fully characterized by 1H, 19F, and 13C NMR, and an X-ray crystal structure

was obtained for bis-naphthalene adduct, 20. Again, the highly shielded aromatic protons

of the AF4 benzene ring that face the endo benzene rings of adducts 20 and 21( 6 =5.24

and 5.38 ppm, respectively) are noted with interest.

Table 2-2. Diels-Alder reactions from treatment of 4, 15-diodo-octafluoro
[2.2]paracyclophane, 18, with potassium t-butoxide, in refluxing solvent.
Substrate Solvent Temperature Time Product

(C) (minutes) (%)

benzene benzene reflux (80) 150 19(83)

naphthalene butyl ether reflux (142) 30 20 (86)

anthracene t-butylbenzene reflux (169) 30 21(80)

[2.2]paracyclophane t-butylbenzene reflux (169) 30 22 (84)


2.2.4 NMR Discussion.100

The structural integrity of most compounds and the stereochemistry of compounds

4, 6, and 12 a&b were demonstrated by NMR. The numerous nOes' on such rigid

structures were diagnostic for stereochemical assignment. Of the three pairs of vicinal

protons originating from compound 2 (e.g., 6.47 and 6.47, 7.18 and 7.22, and 6.73 and

6.78 ppm for adduct 14), the one on the formerly benzyne ring (6.47 and 6.47 ppm) can

be identified by its couplings to the carbons at ca. 147 ppm, carbons that in turn couple to

protons originating from the arene (4.54, 4.48, 5.63, and 5.94 ppm) NOes with this pair

(6.47 and 6.47 ppm) identified the pair (7.18 and 7.22 ppm) syn to it. Long-range

couplings between the protons and the carbons in the para-phenylene ring of 14 allowed










the assignment of the pair anti to the protons originating in the benzyne ring of 1 (6.73

and 6.78 ppm, meta to 7.22 and 7.18 ppm, correspondingly).

F F
I F F
benzene
F F 120.2
F F t-BuOK, reflux 27.05
F F138.0
F 6.29
SF 124.6 126.8/ 5.48
| 45.6
FF F 146.8
m, or p-diiodo AF4 F 6.78
19

S F 7.20 F F 7.19
125.6119.9 125.3
S120 / 124.9 1 126.4
.24 F/ 7.53/ F .38 F F 7.59
S124. 27.5 1438 124. 28. 143.1
F \ 5.69 F
47.4 144.6 144.4
F 153 1409 F F 5.96 124.4
F 6.89 50.4 7.30
126.0
6.94
20 21



FF F
2.77 3.08
/ 5 96 2.49 3.05
F F 5.98 F F
F F 6.0 5.87 7.0 6.92

93 6. 93
F F F F 4.44 5.61

2.39 2.56
22a 22b 2.20 2.96

Figure 2-10 The bis-Diels-Alder reaction of AF4-yne

In compound 14, 6.78 displayed a nOe with 5.94 and 4.48 ppm, which in turn displayed

nOe's with 7.07 and 6.96 ppm. Other NOEs afforded positive stereochemical assignment

of the aliphatic protons, e.g., 2.88 ppm displayed nOe's with 5.94, 6.78, and 7.07 ppm.

Compounds 22 a&b were analyzed as a mixture. The fragments originating from

[2.2]paracyclophane displayed very similar proton chemical shifts in both 14a and 14b.









The protons originating from the fluorinated aryne 1 display two ABs of roughly the

same intensity (6.04, 5.96 and 6.01, 5.98 ppm) indicative that 22a and 22b are formed in

equal amounts. Low solubility precluded obtaining ghmbc spectra. The structural

integrity of these compounds was confirmed by nOe's similar to those observed for

compound 14.

For the furan adducts 12 a&b, the major isomer was assigned as 12a on the basis of

the nOes' between the protons at 6.76 ppm (identified as anti to the protons originating

from the aryne ring of 1 as mentioned above) and the protons at 7.29 ppm, originating in

the furan.

Isomer 6 would be expected on steric grounds, and the exo-structure was

unambiguously confirmed on the basis of nOe's that were observed between the

cyclophane protons that are pointed toward the former tert-butylbenzene (6.97 and 6.90

ppm) and the vinylic protons at 7.02 and 7.06 ppm.

In a similar fashion, in compound 4, the proton at 5.78 ppm displays nOe's with

those at 7.27 and 7.59 ppm and no nOe with the alkene proton at 6.93 ppm, proof for the

endo stereochemistry.

2.2.5 X-ray Discussion.

Some of adducts were analyzed by X-ray diffraction (Appendix). Crystal structures

of anthracene adduct and bis-naphthalene adduct were demonstrated below. The crystal

structure of the anthracene adduct 5 (Figure 2-11 and also Appendix Figure 2) indicates

that, although there are several ways for the AF4 moiety to be distorted upon derivation,

the main impact is that the torsion angles around the bridging C7-C8 and C15-C16

moieties (for example, the C6-C7-C8-C9 torsion angle, as seen in Figure 2-11) open to









values of 26.5 and 27.0 respectively. This is accomplished by twisting the phenyl rings

by an angle of 11.6 around an axis perpendicular to them.















Figure 2-11 ORTEP drawing of anthracene adduct 5 and endo furan adduct 12a

According to the X-ray structure of endo furan adduct, 12a (Figure 2-11 and also

Appendix Figure 3), the distortion parameters of its AF4 moiety involve bridging torsion

angles of 12.6 and 21.9 with a twist angle of 7.7 whereas for [2.2]paracyclophane

adduct 14 (Figure 2-12 and also Appendix Figure 1), the bridging torsion angles are 14.1

and 22.1 two phenyl rings of AF4 moiety have a twist angle of 14.90 connected to

[2.2]paracyclophane and 8.10 on the other one.














Figure 2-12 ORTEP drawing of [2.2]paracyclophane adduct 14 and bis naphthalene
adduct 20
1C. 11 2C',






Figure 2-12 ORTEP drawing of [2.2]paracyclophane adduct 14 and bis naphthalene
adduct 20









The X-ray analysis of bis-naphthalene adduct 20 (Figure 2-12 and also Appendix

Figure 4) indicates that there are two molecules of 20 in its asymmetric unit. For

molecule A, the bridging torsion angles are 28.0 and 30.1 with a twist angle of 12.4 ,

whereas for molecule B the bridging torsion angles are 27.7 and 28.9 with its twist

angle being 23.1 .


In summary, there is a trend observed in these X-ray structures when considering

how the AF4 moiety is distorted in order to relieve the strain of adding a large substituent

to the benzene rings. Small variations in the dihedral angles between the benzene rings of

each of the four crystal structures of from 1.2 to 4.9 are observed. More significantly,

and presumably in order to minimize nonbonded interactions, the benzene rings twist

around an axis perpendicular to the benzene rings, with more twist being observed for

larger substituents. Such twist is coupled with an opening of the bridging torsion angles

of the CF2-CF2 units.

2.3 Conclusion

On the basis of the results that have been presented, it can be concluded that the

reactive arynes, 1 and 17, have been generated and are responsible for the chemistry

observed and discussed. The relative ease of their generation refluxingg benzene) can be

ascribed to an increase in acidity of the proton vicinal to the halogen, induced by the

highly electronegative fluorinated bridges. The fluorinated bridges of 1 and 17 should

also make them highly electrophilic and therefore more reactive arynes (compared to the

nonfluorinated dehydro[2.2]paracyclophane). However, such high electrophilicity should

also lead to enhanced reactivity with nucleophiles such as t-butoxide ion, which is not

observed. At this time, the only potential explanation we have for the chemoselectivity









exhibited by arynes 1 and 17 is the possible electrostatic repulsion of the t-butoxide

nucleophile by the fluorinated bridges of the two arynes. The base used in aryne reactions

above is not soluble in above system, which means that reactions occur heterogeneously.

Heterogeneous characteristics may also explain the absence oft-butoxide ion addition

product, which is a major product in Cadogan's early report. Other aspect of the reaction

mechanism will be discussed further in the next chapter.


2.4 Experimental

General Methods. H (500 MHz), 13C (126 MHz), and 19F (282 MHz) NMR

spectra were recorded using CDC13 as the solvent, and chemical shifts (6 values) were

measured relative to the signals for CHC13, CDC13, and CFC13, respectively. 1H and 13C

chemical shift data are directly indicated on the structures of the adducts in the Results

and Discussion section above, whereas 19F NMR data are provided in the Experimental

Section below. X-ray crystal analyses were performed by the Center for X-ray

Crystallography and HRMS and CH micro elemental analyses by the Spectroscopic

Services Group at the University of Florida. Column chromatography was performed

using chromatographic silica gel, 200-425 mesh, as purchased from Fisher, unless

otherwise mentioned.


4-Nitro-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane. Into 200 mL of 90%

nitric acid was added 10.0 g (2.8 mmol) of AF4 in one batch. The mixture was stirred

overnight, after which it became a clear solution. This solution was then added to 500 g

of ice in an Erlenmeyer flask, and a white precipitate formed. The mixture was filtered to

give 10.0 g (90%) of the yellow-white mononitro product, 23.52









Isomeric Dinitro-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophanes. Explicitly

following the published procedure,51 22.1 g (166 mmol) of nitronium tetrafluoroborate

undergoes reaction with 10.2 g (29 mmol) of AF4 in sulfolane (100 mL) in an overnight

reaction at 80"C to form a white solid product when poured into ice. Column

chromatography (hexane/ethyl acetate, 10:1) gave 6.3 g (49%) of an almost 1:1 mixture

of the 4,15- and 4,16-dinitrooctafluoro[2.2]paracyclophanes, 25a and 25b, respectively,

along with 3.0 g (23%) of the 4,12-dinitro isomer.


4-Amino-l,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane, 24. A anhydrous

methanol (100ml) solution of 23 (3.0 g, 7.6 mmol) was added ammonium format (7.2g,

114mmol) and Pd/C (0.24g, 0.23mmol) under nitrogen at room temperature.101 The

mixture was purged with hydrogen three times, and then a hydrogen balloon was attached

to it. After stirring the reaction mixture overnight, solution was filtered over a short pad

of silica Gel. The solvent was evaporated to give 2.55 g amine 24 in yield of 91%.


Mixture of 4,15- and 4,16-Diamino-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclo-

phanes, 26a and 26b. Likewise, 0.51 g (1.15 mmol) of the mixture of 25a,b was

converted to 0.39 g (89%) of a mixture ofpseudo-meta and pseudo-para diamines, 26a

and 26b, respectively.


4-Iodo-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane, 2.52 A solution of amine

16 (1.9 g, 5.2 mmol) in acetic acid (4 mL) was cooled to 0C in an ice/brine bath. Ice (1.5

g) and 1.5 mL of H2SO4 were added with stirring, and ensuring that the temperature was

still below 0C, Na NO2 (2.0 g, 29 mmol) was added in one batch. After the reaction was

stirred for 2 h at 0OC, it was poured, with vigorous stirring, into 10 mL of an aqueous









solution of KI (5.2 g, 30.8 mmol) at room temperature. After stirring overnight, the

mixture was filtered and the solid purified by column chromatography (alumina,

hexane/EtOAc, 50:1) to give 1.7 g (67%) of the 4-iodo product, 2.


Mixture of 4,15- and 4,16-Diiodo-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclo-

phanes, 18a and 18b.51 A solution of the mixture of 4,15- and 4,16-diaminooctafluoro

[2.2]paracyclophanes, 26a and 26b, respectively, (2.0 g, 5.2 mmol) in acetic acid (4 mL)

was cooled to 0C in an ice/brine bath; ice (1.5 mL) and concentrated sulfuric acid (1.5

mL) were added with stirring. With the temperature maintained below 0 C, sodium nitrite

(2.0 g, 29.0 mmol) was added as quickly as possible to the solution. The reaction was

stirred at this temperature for 2 h, and then the mixture was added to an aqueous solution

(10 mL) of potassium iodide (5.2 g, 30.8 mmol) at room temperature with vigorous

stirring. This mixture was kept stirring at room temperature overnight and then filtered

with the solid being purified by column chromatography (hexane/ethyl acetate, 50:1) to

give 2.2 g (68%) of a mixture of 18a and 18b.


Generation of 4,5-Dehydrooctafluoro[2.2]paracyclophane, 1, and its Reaction

with [2.2]Paracyclophane. Into a three-necked round-bottomed 50 mL flask were added

iodide 2 (0.478 g, 1 mmol) and potassium t-butoxide (0.56 g, 5 mmol) along with 10 mL

of dry t-butylbenzene under a nitrogen flow. Then, [2.2]paracyclophane (0.22 g, 1.1

mmol) was added and the mixture heated to 170"C and refluxed for 20 min. The oil bath

was then removed and the reaction product mixture examined by 19F NMR. The reaction

was worked up by filtering the mixture through a short pad of silica Gel, washed with

3X10 ml dichloromethane. Solvent was evaporated away, and products were further









purified through silicon Gel column to give 86% yield of 8: mp 140-142C; 1H NMR

(500MHz) (CDC13/TMS): 6 7.22(d, J=8.7Hz, 2H), 7.18(d, J=8.4Hz, 1H), 7.07, 6.96(ABX,

J=8.2, and 1.5Hz, 2H), 6.95, 6.93(ABX, J=8.1, 1.5Hz, 2H), 6.78, 6.73(AB, J=8.6Hz, 2H),

6.47(s, 2H), 5.94(d, J=6.2Hz, 1H), 5.63(d, J=6.6Hz, 1H), 4.54(ABX, J=6.3, 2.8Hz, 1H),

4.48(ABX, J=6.2, 1.8Hz, 1H), 3.12(ABX, J=12, 7.1, 2.6Hz, 1H), 2.98(ABX, J=13.2, 8.0,

4.0Hz, 1H), 2.88(m, 1H), 2.82 (DT, J=13.1, 7.9Hz, 1H), 2.58, 2.55(AB, J=7.9Hz, 2H),

2.38(ABM, J=15.1, 8.1, 4.1, 2.0Hz, 1H), 2.20(ABX, J=15.2, 8.1, 0.6Hz, 1H); 19F

NMR(282MHz, CDC13/CFC13), four equal intensity AB quartets at 6-111.4 (J= 244.2 Hz)

and -111.7 (J= 243.9 Hz), -115.0 (J= 243.9 Hz) and -115.7 (J= 244.2 Hz), -116.7 (J=

239.7 Hz) and -117.7 (J= 241.1 Hz), -119.4 (J= 240.8 Hz) and -119.9 (J= 239.7 Hz);

HRMS calcd for C32H22F8 558.1594, found 558.1594.


Reaction of Aryne 1 with Anthracene. The procedure is the same as above, except

that 0.18 g (1.1 mmol) of anthracene was used and the reaction was refluxed for 15 min.

Two isomers, in a ratio of 93:7 (from 19F NMR) were obtained in a total yield of 84%.

The major isomer was isolated via silica gel chromatography (hexane/EtOAc, 100:1).

Major isomer (5): mp 296-298C; 1H NMR (300MHz, CDC13/TMS) 6 Isomer 1 7.65(m,

2H), 7.32(m, 2H), 7.27(m, 2H), 7.20(s, 2H), 6.96(m, 2H), 6.72(s, 2H), 6.01(s, 2H), 5.84(s,

2H); 13C NMR(126MHz, CDC13) 6 144.4, 142.7, 134.0, 128.9, 128.7, 128.2, 127.9, 126.1,

125.7, 124.5, 120.0, 118.7, 50.3; MS(EI): 528(M+, 76), 352, 301, 176, 69; 19F NMR

(282MHz, CDC13/CFC13), two equal intensity AB quartets at E-111.4 (d, J= 243.9 Hz)

and -115.1 (d, J= 243.9 Hz), -116.53 (J= 240.8 Hz) and -119.4 (d, J= 240.8 Hz); Anal.

Calcd for C30H16Fs: C, 68.18, H, 3.05. Found: C, 67.73; H, 2.86. Minor isomer: Isomer 2

7.76(s, 2H), 7.78(m, 2H), 7.52(m, 2H), 7.30(m, 2H), 7.18(s, 2H), 6.94(m, 2H), 5.80(m,









2H), 5.64(s); 19F NMR(282MHz, CDC13/CFC13), two equal intensity AB quartets at S-

111.1 (d, J= 243.9 Hz) and -115.4 (d, J= 243.9 Hz), -116.3 (d, J= 237.7 Hz) and -119.5

(d, J= 240.8 Hz).


Reaction of Aryne 1 with Benzene. The procedure is the same as above, except

that the reaction was carried out in refluxing benzene at 80 C for 150 min. The product

was purified by silica gel chromatography (hexane/EtOAc, 100:1) with a 86% yield of 3:

mp 144-146C; 1H NMR (500MHz, CDC13) 6 7.26(s, 2H), 7.05(AB, J=3.3, 4.2Hz, 2H),

6.91(d, J=1.1Hz, 2H), 6.78(dd, J= 3.0, 4.5Hz, 2H), 6.60(s, 2H), 5.48(m, 2H); 19F

NMR(282MHz, CDC13/CFC13), two equal intensity AB quartets, 6-111.9 (d, J= 247.0 Hz)

and -115.7 (d, J= 244.0 Hz), -117.79 (d, J= 240.8 Hz) and -119.54 (d, J= 240.8 Hz);

MS (El) 428 (M+), 368, 252, 192, 176 and 57; 13C NMR(126MHz, CDC13) 6 146.8, 141.8,

137.6, 134.1, 128.9, 128.8, 127.3, 126.3, 45.7; HRMS calcd for C22H12F8 428.0811,

found 428.0811. Anal. Calcd for C22H12Fs: C, 61.69; H, 2.83. Found: C, 61.52; H, 2.69.


Reaction of Aryne 1 with t-Butylbenzene. The procedure was identical to those

above, except that the reaction was carried out using refluxing tert-butylbenzene (bp 169

"C) as both a solvent and a reactant. The product was purified by silica gel

chromatography (hexane/EtOAc, 100:1) with the yield of 6 being 78%: mp 131-133 C;

1H NMR (500MHz, CDC13/TMS) 6 7.28(d, J=8.4Hz, 1H), 7.24(d, J=8.4Hz, 1H), 7.06(m,

1H), 7.02(m, 1H), 6.97(d, J=8.7HzHz, 1H), 6.90(d, J=8.7Hz, 1H), 6.62(s, 2H), 6.19(d,

J=6.2Hz, 1H), 5.49(d, J=5.6Hz, 1H), 5.39(m, 1H), 0.91(s, 9H); 19F NMR (282MHz,

CDC13/CFC13), four equal intensity AB quartets at 6-111.4 (J= 243.9 Hz) and -112.5 (J=

243.9 Hz), -115.3 (J= 243.9 Hz) and -115.9 (J= 243.9 Hz), -117.2 (J= 240.8 Hz) and -









119.8 (J= 240.8 Hz), -118.4 (J= 241.1 Hz) and -119.4 (J= 240.8 Hz); 3C NMR

(126MHz, CDC13) 147.5, 147.3, 138.3, 137.4, 134.3, 133.9, 130.3, 129.0, 128.9, 128.6,

126.9, 126.6, 126.3, 126.2, 120.0, 46.8, 45.5, 34.7, 27.6; Anal. Calcd for C26H20Fs: C,

64.46; H, 4.17. Found: C, 64.22; H, 4.22.


Reaction of Aryne 1 with Naphthalene. The procedure was carried out as above

except that di-n-butyl ether (bp 142C) was used as the solvent and naphthalene as the

substrate (0.14 g, 1.1 mmol). Refluxing for 30 min provided a mixture of products (ratio

>10:1), which after chromatography in the usual manner gave major product endo-adduct

4 in a yield of 88%: mp 204-206"C; 1H NMR (300MHz, CDC13/TMS) 6 7.59(m, 2H),

7.27(m, 2H), 7.22(s, 2H), 6.93(m, 2H), 6.70(s, 2H), 5.78(s, 2H), 5.75(s, 2H); 13C NMR

(126MHz, CDC13) 145.2,143.3, 141.2, 133.9, 130.0, 128.8, 127.58, 127.0, 125.8, 125.3,

47.5; 19F NMR(282MHz, CDC13/CFC13), two equal intensity AB quartets, 6-111.2, -115.5

(JAB = 243.9 Hz), and 8-116.4, -119.5 (JAB = 247.0 Hz); HRMS calc 478.0967, found

478.0968. Anal. Calc for C26H14F8: C, 65.28; H, 2.95. Found: C, 65.05; H, 2.89. Minor

product (presumably exo-adduct): 19F NMR, two equal intensity AB quartets, 6-112.0, -

115.3 (JAB = 246.8 Hz) and d -117.8, -119.6 (JAB = 236.9 Hz).


Reaction of Aryne 1 with Furan. This reaction was carried out as above in

refluxing tert-butylbenzene for 20 min with furan as the substrate. A mixture of the endo

and the exo-adducts, 12a,b, (ratio = 1:0.6), was obtained in 80% yield. Chromatography

in the usual manner provided partial separation of the isomers, such that small amounts of

individual, pure isomers could be obtained, along with larger amounts of mutually

contaminated fractions. endo-Isomer, 12a: mp 162-163.5C; 1H NMR (300MHz,









CDC13/TMS) isomerl 6 7.33(s, 2H), 7.22(s, 2H), 6.99(d, J=0.9Hz, 2H), 6.65(s, 2H),

5.91(d, J=3.9Hz, 2H); 13C NMR (126MHz, CDCl3)6 150.4, 144.1, 134.8, 129.7, 129.2,

127.6, 127.3, 119.4, 118.9, 81.0; 19F NMR(282MHz, CDC13/CFC13), two equal intensity

AB quartets, 6-112.6, -119.2 (JAB = 243.9 Hz), 6-116.1, -117.9 (JAB = 240.8 Hz); HRMS

calcd for C20HioF8 418.0604, found 418.0604. exo-Isomer, 12b: H NMR (300MHz,

CDC13/TMS) 6 7.41(s, 2H), 7.29(s, 2H), 6.76(s, 2H), 6.51(s, 2H), 5.88(m, 2H); 13C NMR

(126MHz, CDCl3)6 147.5, 140.6, 134.2, 128.8, 128.5, 127.9, 127.7, 119.3, 118.7; 19F

NMR(282MHz, CDC13/CFC13), two equal intensity AB quartets, E-111.9, -114.3 (JAB

243.9 Hz), 6-116.2, -118.0 (JAB = 238.0 Hz).


Reaction of Aryne 1 with Bicyclo[2.2.1]hepta-2,5-diene: The procedure was

carried out as above except that di-n-butyl ether (bp 142C) was used as the solvent and

bicyclo[2.2.1]hepta-2,5-diene (0.043g, 50ul, 0.46mmol) was used as the substrate (0.14 g,

1.1 mmol). A mixture of products (ratiol5a:15b:16a:16b=62:27:3:8) was obtained after

refluxing for 30 min. A product mixture (75 mg) was obtained in a total 67% yield after

chromatography in the usual manner, which includes four different isomers: exo- and

endo-1,4-addition products 15a&b, endo- and exo-1,2- addition products 16a&b with a

ratio of 62:27:3:8. Spectrum of 15a: 1H NMR (500MHz, CDC13/TMS) 6 7.27(s, 2H),

7.14(S, 2H), 6.80(s, 2H), 3.37(s, 2H), 3.05(s, 1H), 1.88(m, 1H), 1.81(m, 2H), 1.12(m,

2H); 13C NMR(126MHz, CDCl3)6 149.9, 135.1, 130.0, 128.3, 127.9, 119.9, 119.1, 56.5,

47.0, 33.7, 23.8, 21.3; 15b: H NMR (500MHz, CDC13/TMS) 6 7.40(s, 2H), 7.02(s, 2H),

6.65(s, 2H)s,3.40(s, 2H), 2.04(m, 1H), 1.88(m, 1H), 1.78(m, 1H), 1.66(s, 2H); 13C

NMR(126MHz, CDC13) 6 145.3, 134.5, 128.8, 128.8, 128.2, 127.8, 119.6, 118.8, 56.4,









49.0, 31.0, 25.2, 19.9; 19F NMR (282MHz, CDC13/CFC13)6 -110.5 (d, J=240.83Hz), -

111.9 (d, J=240.83Hz), -112.79(d, J=241.11Hz), -114.09(d, J=247.03Hz), -114.98(d,

J=237.73Hz), -115.04(d, J=240.83Hz), -115.15 (d, J=237.73Hz), -116.16 (d, J=238.0), -

116.28 (d, J=241.11Hz), -116.99 (d, J=234.62Hz), -117.14 (d, J=240.83Hz), -117.18 (d,

J=237.73Hz), -118.14 (d, J=237.73Hz), -117.35 (d, J=243.93Hz), -119.16 (d, J=238.0Hz),

-119.69 (d, J=241.11Hz); 16a: 1H NMR (500MHz, CDC13/TMS) 6 7.56(s, 2H), 6.98(s,

2H), 6.62(s, 2H), 6.28(m, 2H), 3.17(s, 2H), 1.92(s, 1H), 1.81(m, 1H); 13C NMR(126MHz,

CDC13) 6 142.7, 136.9, 134.9, 131.1, 126.7, 128.6, 128.9, 126.7, 118.9, 118.6, 50.4, 42.8,

40.3; 16b: 1H NMR (500MHz, CDC13/TMS) 6 7.3 1(s, 2H), 7.23(s, 2H), 6.92(s, 2H),

6.31(m, 2H), 2.88(m, 2H), 2.86(m, 2H), 1.21(s, 1H), 0.73(m, 1H); 13C NMR(126MHz,

CDC13) 6 147.9, 137.1, 134.8, 129.8, 128.9, 128.5, 124.6, 118.4, 118.4, 46.6, 42.7, 41.4;

19F NMR (282MHz, CDC13/CFC13) 6 -111.42 (d, J=244.21Hz), -112.48 (d, J=243.93Hz),

-115.31(d, J=244.21Hz), -115.92 (d, J=244.21Hz), -117.17 (d, J=240.55Hz), -118.35 (d,

J=240.55Hz), -119.40 (d, J=240.26Hz), -119.81 (d, J=240.55Hz); MS(EI) m/z

442(M+)(3), 191(100), 176(63), 126(13). HRMS Calc. for C23H14F8 442.0967, Found

442.0974 (EI).


When pure bicyclo[2.2.1]hepta-2,5-diene is used as solvent and reactant, the ratio of

15a:15b:16a:16b is 74:12:10:4. Isomer 15a is separated from the others by

chromatography and has a melting point of 233-235 C.


Reaction of Aryne 1 with 1,4-Dimethylnaphthalene: The procedure was carried

out as above except that 1,4-dimethylnaphthalene (0.10 g, 0.6mmol) was used as the

substrate. A mixture of products (ratio 3.43:1) was obtained after refluxing for 30 min,









which after chromatography in the usual manner gave major product endo-5,8-adduct 7

in a yield of 60%. Endo- product: 1H NMR (500MHz, CDC13/TMS) 6 7.07(s, 2H), 6.86(s,

2H), 6.79(m, 2H), 6.51(s, 2H), 5.92(s, 2H), 5.65(s, 2H), 2.49(s, 6H); 13C NMR(126MHz,

CDCl3) 6 145.4, 141.6, 141.4, 134.4, 131.3, 128.6, 128.6, 127.9, 127.5, 127.4, 120.4,

119.1, 43.9, 18.1; 19F NMR (282MHz, CDC13/CFC13) 6 -108.94, -114.22 (AB,

J=243.93Hz, 4F), -114.76, -118.48 (AB, J=238.01, 4F); Exo- product: 1H NMR (500MHz,

CDC13/TMS) 6 7.13(s, 2H), 7.06(s, 2H), 6.91(s, 2H), 6.55(s, 2H), 6.54(s, 2H), 5.87(m,

2H), 2.23(s, 6H); 13C NMR(126MHz, CDC13) 6 145.7, 143.6, 137.6, 137.5, 134.2, 130.1,

129.4, 129.0, 127.4, 126.5, 120.1, 119.0, 44.2, 18.1; 19F NMR (282MHz, CDC13/CFC13) 6

-111.86, -115.20 (AB, J=243.93Hz, 4F), -117.74, -119.21 (AB, J=240.83Hz, 4F); MS(EI)

m/z 506(M+)(99), 330(100), 176(8); HRMS Calc. for C28H18sF 506.1280, Found

506.1293 (EI). The stereochemistry was proven by the nOe's between 2.49 and 5.65 in

the major and between 7.06 and 6.91 in the minor.


Reaction of Aryne 1 with 2,3-Dimethylnaphthalene: the procedure was carried

out as above except that 2,3-dimethylnaphthalene (0.10 g, 0.6mmol) was used as the

substrate. A sole endo product was obtained after refluxing for 30 min, which after

chromatography in the usual manner gave major product endo-adduct 8 (85 mg) in a

yield of 67%. Solid starts to decompose at 168C. 1H NMR (300MHz, CDC13/TMS) 6

7.53 (m, 2H), 7.24(m, 2H), 7.17(d, J=1.2Hz, 2H), 6.67(s, 2H), 5.71(s, 2H), 5.27(d,

J=1.8Hz, 2H), 1.71(s, 6H); 19F NMR (282MHz, CDC13/CFC13) 6 -111.19, -114.90 (AB,

J=243.93 Hz, 4F), -116.44, -119.42 (AB, J=237.73Hz, 4F); 13C NMR(75MHz, CDC13) 6

144.9, 143.1, 141.2, 133.9, 128.9, 127.9, 127.6, 127.1, 125.7, 124.7, 120.0, 118.7, 53.5,









16.5; MS(EI) m/z 506(M+)(77), 330(100), 176(14); HRMS Calc. for C28H18F8 506.1280,

found 506.1288 (El).


Reaction of Aryne 1 with 2-Methoxynaphthalene: the procedure was carried out

as above except that 2-dimethoxylnaphthalene (0.11 g, 0.7mmol) was used as the

substrate (0.14 g, 1.1 mmol). A product mixture of was obtained after refluxing for 30

min, which after chromatography in the usual manner gave three products.

Isomer 9, 18%: 1H NMR (300MHz, CDC13/TMS) 6 7.44(dd, J=8.1, 2.1Hz, 1H),

7.20(S, 2H), 7.17(t, J=2.5Hz, 1H), 6.90(m, 2H), 6.73(dd, J=8.1, 2.4Hz, 1H), 6.66(s, 2H),

5.83(dd, J=9.3, 12.6Hz, 2H), 5.64(d, 4.8Hz, 2H), 3.86(s, 3H) 19F NMR (CDC13/CFC13) 6

-111.20, -115.45(AB, J=243.9Hz, 2F), -111.27, -115.48(AB, J=245.4Hz, 2F), -116.23, -

119.48(AB, J=237.7Hz), -116.35, -119.63(AB, J=242.5Hz, 2F) 13C NMR (75MHz,

CDC13) 6157.98, 145.38, 145.28, 144.99, 141.75, 140.83, 135.31, 133.94, 128.74, 128.42,

128.10, 127.64, 127.44, 127.10, 126.17, 125.61, 125.44, 124.20, 123.19, 119.93, 118.65,

112.54, 109.64, 102.16, 55.92, 47.50, 46.53. MS(EI) m/z C27H16F80 508(M+)(77),

332(71), 276(35), 176(100); HRMS Calc. for C27H16F80 508.1073, Found 508.1075 (EI).

Isomer 10, 4%: 1H NMR (500MHz, CDC13/TMS) 6 7.18(t, J=5.8Hz, 2H), 7.12(d,

J=8.1Hz, 1H), 7.09(d, J=7.2Hz, 1H), 7.02(d, J=8.1Hz, 1H), 6.91(s, 2H), 6.76(d, J=2.4Hz,

1H), 6.60(s, 2H), 6.34(dd, J=8.0, 2.5Hz, 1H), 5.58(dt, J=6.6, 1.18Hz, 1H), 5.57(dt, J=6.01,

1.86Hz, 1H), 3.69(s, 3H); 19F NMR (282MHz, CDC13/CFC13) 6 -111.98 (d, J=243.93Hz,

1F), -112.05 (d, J=243.93Hz, 1F), -115.37(d, J=243.93Hz, 1F), -115.22(d, J=243.93Hz,

1F), -116.8 (d, J=241.11Hz, 1F), -116.91(d, J=238.01Hz, 1F), -119.26(d, J=237.73Hz,

1F), -119.44(d, J=237.73Hz, 1F); 13C NMR (126MHz, CDC13) 6 157.2, 146.9, 146.0,

145.4, 138.1, 137.4, 137.1, 127.8, 127.8, 127.5, 127.5, 134.1, 134.1, 129.3, 129.3, 128.9,









128.9, 124.4, 111.2, 109.4, 55.8, 47.9, 46.9; MS(EI) m/z 508(M+)(100), 332(90), 176(18);

HRMS Calc for C27H16F80 508.1073, Found 508.1068 (El).

Isomer 11, 27%: 1H NMR (300MHz, CDC13/TMS) 6 7.65 (tt, J=6.9, 1.8Hz, 2H),

7.48(m, 2H), 7.17(s, 2H), 7.02(s, 2H), 5.75(dd, J=24.6, 8.7Hz, 2H), 5.40(s, 1H), 5.20(t,

J=2.7Hz, 1H), 2.02, 2.29(AB, J=18.3, 2.7Hz, 2H). 19F NMR (282MHz, CDC13/CFC13) 6 -

111.67 (d, J=247.03Hz, 1F), -112.16 (d, J=247.03Hz, 1F), -114.68 (d, J=246.75Hz, 1F), -

115.45(d, J=243.93Hz, 1F), -117.05 (d, J=238.0Hz, 1F), -117.22 (d, J=241.11Hz, 1F), -

119.32(d, J=240.83Hz, 1F), -119.40(d, J=240.83Hz, 1F); 13C NMR(75MHz, CDC13) 6

202.04, 142.0, 140.0, 135.7, 134.5, 134.3, 134.0, 133.6, 130.3, 130.0, 129.7, 129.0, 128.7,

128.2, 128.0, 127.9, 127.5, 125.79, 125.77, 123.7, 122.1, 119.7, 118.5, 59.2, 41.8, 37.9;

MS(NBA-C3) m/z 495 [M+H]+(13), 452(17), 276(24); HRMS Calc for C26H13F80 (M+H)

495.0995, Found 495.1970 (NBA-C3).

Reaction of Aryne 1 with 2,5-Diphenylbenzofuran: the procedure was carried out

as above except that 2,5-diphenylbenzofuran (0.11 g, 0.Smmol) was used as the substrate.

A product mixture (ratio exo: endo=84:16) was obtained after refluxing for 30 min, which

after chromatography in the usual manner gave major product exo-adduct 13a and endo-

adduct 13b in a yield of 71% and 14% respectively. Exo-product gets soft at 220-222C

and decompose at temperature above 240 C, while endo-adduct decompose at 192C.

Exo-Isomer: 1H NMR (500MHz, CDC13/TMS) 6 7.85(m, 4H), 7.56(t, J=7.7Hz, 4H),

7.50(t, J=7.6Hz, 2H), 7.33(s, 2H), 7.25(s, 2H), 7.20(, s, 2H), 6.64(s, 2H); 13C

NMR(126MHz, CDC13) 6 152.6, 148.3, 135.0, 135.0, 130.2, 128.3, 128.3, 128.3, 127.7,

127.2, 127.2, 127.2, 119.1, 118.6, 94.7; 19F NMR (282MHz, CDC13/CFC13) -113.18(d,

J=250.13Hz, 2F), -114.19(d, J=249.85Hz, 2F), -116.73(d, J=243.93Hz, 2F), -120.70(d,









J=243.93Hz, 2F); endo-Isomer: 6 1H NMR (500MHz, CDC13/TMS) 6 7.84(s, 4H),

7.54(m, 4H), 7.48(s, 2H), 7.43(m, 2H), 6.98(s, 2H), 6.60(s, 2H); 13C NMR(126MHz,

CDC13) 6153.0, 142.7, 136.2, 133.7, 129.5, 128.8, 128.7, 128.4, 128.2, 128.0, 118.5,

118.2; 19F NMR (282MHz, CDC13/CFC13) 6 -106.25(d, J=238.01Hz, 2F), -109.26(d,

J=237.73Hz, 2F), -114.60(d, J=234.91Hz, 2F), -118.96(d, J=234.62Hz, 2F); MS(EI) m/z

570(M+)(6), 176(3), 105(100); HRMS Calc for C32H18F80 570.1230, Found 570.1239

(EI).

Reaction of Bis-aryne 17 with Benzene: the analogous procedure was carried out

by using 0.60 g (1 mmol) of the isomeric diiodides, 18a and 18b, and 1.12 g (10 mmol)

of potassium t-butoxide. This mixture was refluxing in 10 mL of benzene for 2.5 h and

product was purified by silica gel chromatography (hexane/EtOAc, 100:1) to give 0.42 g

(83%) of the bis-adduct 19. Mp> 315C; 1H NMR (CDC13/TMS) 6 6.98(m, 4H), 6.73(m,

4H), 6.22(s, 4H), 5.41(m, 4H); 13C NMR (CDC13/TMS) 6 146.8, 141.5, 138.0, 126.8,

124.6, 120.2, 45.6; 19F NMR(282MHz, CDC13/CFC13), one AB quartet, E-110.9, -115.5

(JAB = 243.9 Hz); HRMS Calc for C22H16F8 504.1124, found 504.1120.


Reaction of Bis-aryne 17 with Naphthalene: The reaction was carried out as in

the preceding example, except that the solvent was 10 mL of di-n-di-n-butyl ether, and

0.28 g (2.2 mmol) of naphthalene was added as the substrate. The mixture was refluxed at

142"C for 30minutes. The residue was purified by silica gel chromatography

(hexane/EtOAc, 100:1) to give 0.52 g (86%) of white solid, bis-adduct 20. Mp 253 C

(dec.); 1H NMR (300MHz, CDC13/TMS) 6 7.53(m, 4H), 7.20(m, 4H), 6.89(m, 4H),

5.69(m, 4H), 5.24(s, 4H); 13C NMR (126MHz, CDC13) 145.3, 143.8, 140.9, 127.5, 125.6,









124.9, 124.3, 120.0, 47.4; 19F NMR (282MHz, CDC13/CFC13), one AB quartet, E-108.9, -

115.0 (JAB = 243.9 Hz); HRMS Calc 604.1437, found 604.1437. Anal. Calc for C36H20F8:

C, 71.52; H, 3.33. Found: C, 71.10; H, 3.28.


Reaction of Bis-aryne 17 with Anthracene: The procedure was the same as in the

preceding examples, except that the reaction was carried out for 30 min at 169C in 10

mL of refluxing t-butyl benzene, using 0.39 g (2.2 mmol) of anthracene as a substrate.

The product was purified by silica gel chromatography (hexane/EtOAc, 100:1) with 0.56

g (80%) of the bis-adduct, 21, being obtained: mp > 310C; 1H NMR (300MHz,

CDC13/TMS) 6 7.59(m, 2H), 7.29(m, 2H), 7.19(m, 2H), 6.38(m, 2H), 5.96(s, 2H), 5.37(s,

2H); 19F NMR (282MHz, CDC13/CFC13), one AB quartet, 6-109.1, -114.7 (JAB = 243.9

Hz); HRMS calcd for C44H24F8 704.1744, found 704.1748.


Reaction of Bis-aryne 17 with [2.2]Paracyclophane: The procedure was carried

out in refluxing t-butylbenzene, as in the previous example, and 0.46 g (2.2 mmol) of

[2,2]paracyclophane was used as a substrate. The crude product was purified by silica gel

chromatography (hexane/EtOAc, 100:1), a 50:50 mixture of the diastereoisomeric bis-

adducts 22a and 22b, 0.64 g (84%) white solid was obtained: mp 315 C (dec.); 1H NMR

(300MHz, CDC13/TMS) 6 7.03(d, J=7.8, 2H), 6.94(d, J=8.4Hz), 6.93(s, 4H), 6.05(d,

J=8.4, 2H), 5.97(d, J=8.4Hz, 2H), 5.89(d, J=6.3Hz, 2H), 5.62(d, J=6.0Hz, 2H), 4.51(m,

2H), 4.44(m, 2H), 3.09(m, 2H), 2.99(m, 2H), 2.78(m, 4H), 2.54(m, 4H), 2.38(m, 2H),

2.23(m, 2H); 13C NMR (126MHz, CDC13) 6 147.07, 142.51, 139.84, 139.62, 137.61,

134.63, 133.03, 128.05, 126.41, 126.08, 125.76, 125.37, 125.04, 124.37, 123.11, 51.59,

51.10, 34.66, 34.24, 33.64, 33.36; 19F NMR (282MHz, CDC13/CFC13) (isomer 1) two






54


equal intensity AB quartets, 6-109.6, -115.0 (JAB = 243.9 Hz), 8-110.9, -115.6 (JAB =

240.8 Hz); (isomer 2) two equal intensity AB quartets, 6-109.7, -115.2 (JAB = 231.8 Hz), 6

-110.6, -115.4 (JAB = 231.5 Hz); HRMS calcd for C48H36F8 764.2689, found 764.2689.












CHAPTER 3
CADOGAN METHOD AND REACTION MECHANISM

3.1 Introduction

N-nitrosoacetanilide was also reported by Cadogan in 1972 to generate benzyne via

decomposition of the intermediate benzene-diazonium salt.102 103 The mechanism that he

proposed is illustrated in Figure 3-1, and in this chapter we will describe the application

of Cadogan's method to the generation of AF4-yne.





N
~-- N=N-0-f'
O-0


+N= NN2 + Ac20
}'


Figure 3-1 Decomposition of benzene-diazonium slat

Aryne chemistry is very important in the synthesis of natural products and has been

well reviewed.66 Three main classes of reactions have been observed: a) Diels-Alder (DA)

addition with 1,3-dienes; b) ene-reaction with alkene possessing a suitable allylic proton;

c) 2+2 cycloaddition.


G) e
N--N 0--r
0









The generation of an aryne by treatment of an aryl halide with potassium t-butoxide

is first reported by Cram, and in this chapter we will describe this procedure as the" Cram

method". In his original study, aryne reactions were carried out in dimethyl sulfoxide,

and the t-butoxide ion adduct was the major product. We have already discussed the 4, 5-

dehydro- and 4, 5, 15, 16-bis(dehydro)- octafluoro [2,2] paracyclophane aryne reactions

generated by potassium t-butoxide with the corresponding iodo- derivatives in Chapter

2.49, 50 High yields of DA products were obtained using the Cram method. When the

Cadogan method is applied to the same system, it will be seen that the two methods gave

essentially the same results with regard to DA reactions. However, in the reaction of

aryne with alkenes, the outcomes are totally different. The latter method gives ene

products whereas the former method gives no ene reactions, but instead a reduced,

octafluoro[2.2]paracyclophane (AF4) product.


3.2 Results and Discussion

3.2.1 The Cadogan Method

Cadogan first reported decomposition of benzene diazonium salt to generate

benzyne in situ in 1972.102 Biphenyl was obtained in up to 80% yields in benzene

solution (radical reaction), but giving 31% of ene products in a reaction with methyl

methacrylate.103 When this method is applied to the AF4 system, it gave results virtually

identical to these obtained via the Cram method, when carried out in the presence of a

diene trap, such as benzene, naphthalene or anthracene. For the Cadogan method, 90%,

93% and 95% yields of DA products were obtained for DA reactions with benzene,

naphthalene and anthracene, respectly, as compared to 86%, 88%, 84% when using the

Cram method. The ratios of product isomers varied a little bit. The ratio of anthracene









adducts changed from 97:3 to 95:5, whereas the naphthalene product mixture contains

15-17% exo-adduct versus 8-10% when using the Cram method.

3.2.2 Ene Reactions

When 4-iodo-octafluoro[2.2]paracyclophane (IAF4) was allowed to react with

potassium t-butoxide and 1-octene in butyl ether or in pure 1-octene as solvent, only the

reduced AF4 was observed. In contrast, AF4-yne generated from the decomposing of 4-

(N-nitroso)-acetamide-octafluoro[2.2]paracyclophane (the Cadogan method) gave ene

product 1 in 83% yield with only minor (5%) amount of reduced product AF4 (Figure 3-

2). The critical step in the generation of aryne in the Cadogan method is the loss of the

proton ortho to the diazonium group. The strong electron withdrawing fluorinated bridge

groups make the proton more acidic and thus easier to lose, making the rate of aryne

generation faster than the radical generation in the AF4 system.

SCF2 O CF2

F2 c CF2 +-NO F2C CNF
HI I H NO
F2C N F2C
O O
S CF2

butyl ether F2C IF2
1-Octene I
F2C

1

Figure 3-2 1-Octene with AF4-yne reaction

When cyclohexene and cylopentene were allowed to react with AF4-yne generated

by the Cadogan method, ene products were obtained in 55% and 53% yields, respectively.

The reaction of AF4 -yne with cyclopentene afforded a 5.6:1 mixture of diastereomers











2a/2b (Figure 3-3), identified by NMR of the product mixture. The structural integrity of

compound 2a was demonstrated by the H1-H1 and H1-C13 (one-bond and long-range)

couplings seen in the DQCOSY, GHMQC and GHMBC spectra, correspondingly.

Couplings of the three aliphatic carbons with both of the alkene protons revealed the

cyclopentene moiety. The couplings of 4.23 with 127.8 and 146.5 and of 5.23 with 146.5

7.08 119.8 5.23 5.65 7.08 119.8 1.15
94 135.0 0F2 135.0 131.1 129.4 1.15
6.88CF 135.0 131.1 35.0CF2 2.24 2.24
S788 4.23 127.3 4.15 34.8 4
\7 1 H 329 H 31.9
135.4 47.0 2.52135.4
2.52 135.4 4
127.8 127.8 130.3
118.0 F2 7.08 6.92 9 30.3 118.0 F2 7.08 6.83 118.9 6.07
129.4 CF2 2.15 129.4 CF2 136.1
2.52 5.86
716 135.4 716 135.4
1 0.3 1 0.3
\ 7.16 7.17
130.3 130.3
135.4
118.9 1 129.4 11 135.4 129.4
7.02 118.9 C 7.04
F2 F2
2a 2b
7.09
F 1.10 1.21 132.6 135 F 5.09 5.53
7.12 F2 1.82 1.43 6.90 / 35.4CF2 131.6 127.6
132.6 135.40 33.7 19.9 129.4 120.0
120.0 3.--71H 1.98
6.93 3.71 H 1.942.01
129.4 \1.94 24.7
\25.2 14 .4 38.4.7
148 38.1 135.4 '__J
F2C35 127.6 126.7 132.1 6.98 2.18 1.75
6.96 119.0 5.82 6.07 7.6 19.0 27.6 22.2
119. 7.04 CF 129.4 CF2
129. CF2 716
1 9.4/ 134.6
7.12 134.6 19.4 134.6
1 9.4
.4 129.4 129.4

7.12 7.09
1190 134.6 129.4 119.0 134.6 129.4
F2 7.03 C 7.00
F2 F2

3a 3b


Figure 3-3 Chemical shifts of cyclopentene and cyclohexene products

demonstrated the connection of the cyclopentene moiety to the AF4 frame. Similar

couplings were seen between the protons and the carbons of the minor diastereomer. The

assignment of the protons and carbons of the AF4 moiety in the major product was based









on the HI-HI and H1-C13 (one-bond and long-range) couplings and the nOe's seen

between the protons of one ring and the protons of another. No such assignments were

possible for the minor product, due to the overlap with the signals of the major.

The relative stereochemistry of the two compounds was assigned based on the

nOe's between the protons of the cyclopentene moiety and the protons on the phenyl

rings. In the major, it is the aliphatic protons at 2.15 and 2.52 which display nOe's with

the protons at 6.92 and 7.16. The proton trans- to 4.23, at 2.15, displays an extra nOe

with 7.02. Conversely, the proton at 5.86 in the minor displays nOe's with the protons at

6.83, 7.17 and 7.04 (the weakest) which were assigned as in Figure 3-3, based on the

nOe's intensity and chemical shifts. A weaker nOe was seen between 4.23 and 6.92. All

these nOe's are consistent with the stereochemistry proposed by MM calculations, which

indicate that in the lowest energy conformation the proton of the cyclopentene (4.23 and

4.15) is in the plane of the benzene ring and facing the closest CF2 group. The other

conformation with the proton in the plane of the benzene ring is ca. 10 kJ/mol higher in

energy.

Similarly, cyclohexene products 3a and 3b were assigned as in Figure 3-3, but the

ratio of two isomers was 1:1.

Surprisingly, when AF4-yne was generated using the Cram method, no ene

products were observed in the presence of 1-octene, or cyclohexene with the reduced

product, AF4, being the only observable product. Even pure 1-octene just gave reduction

to AF4 under the Cram conditions.

The AF4-yne generated under Cadogan conditions reacted with a-methylstyrene to

give the DA adduct 5 (24%) and ene product 4 (37%) (Figure 3-4). Another minor











product alcohol, 6 (4% yield) may arise from the oxidation of ene product during its


purification.

118.8 7.24 118.8
7.02 CF2 127.8 F F
129.6 134.6 7.34
128.8
7.13 7.22 18.8 16247
130.2 12625 47 2.
134.8 // F 18 F 127.1
129.4 F 7 6.13 119.7
118.9 7.09 6.87 11 7 7.23 F F
132.1 129.9
F2C 1 1 .7\ 127.5

140.7 4.08 128.1 1 36
130.4 \ 3.54 145.9 129. 120.5
7 39.28 130. 136.2 2.77
135.4 140.6 126.3 129 20.5
132.1 7.29 F -- F 129.9 132.1
F2C118.8 7.32 118.8
116.2 8.17 7.99
4.67 5.35 133.1 / 123.5
7.55 128.3
125.9 7.64
4

7.25 119.8 F2

7.43
127.0 133. 6

128.9 \
134.8130.5
130.7 CF2
118.9 6.82 6.85 120.0
F2 131./ 131.2 7.27
131. 3.41 138.
934.6 3 134.4

135 .6 38.3 68.2 122.8 7.32
130.4 2.55 7.49
F2C 118.7 7.35 27.9
1.84

6


Figure 3-4 Chemical shifts of products from the reaction of a-methylstyrene with AF4-
yne

3.2.3 2-Methoxynaphthalene Reaction

2-Methoxynaphthalene reacts with IAF4 and KOtBu in butyl ether to produce


products (Chapter 2), the ketone product deriving from hydrolysis of the enol ether


during the reaction or purification. In contrast, when 2-methoxynaphthalene reacts with


AF4-yne generated via the Cadogan method, the major product obtained from the


mixture is anthraceno[2.2]paracyclophane (43%), which had been alternatively


synthesized by the reaction of 3,6-dipyridinyl-1,2,4,5-tetrazine with the AF4-yne









naphthalene adduct (chapter 4). DA reactions on both substituted and unsubstituted ring

were also observed under Cadogan's conditions (total yields are 12%). It must be

assumed that the phenyl anthraceno[2.2]paracyclophane is derived from a retro DA

reaction by losing the methoxyetheno group as showed in Figure 3-5.

CF2




S OF/ C retro DA F2

F2C
2 C F2C
F2


Figure 3-5 Retro Diels-Alder reaction of 2-methoxynaphthalene adduct to phenyl
anthraceno[2.2] paracyclophane

3.2.4 Tetracyclone Reaction

Tetraphenylcyclopentadienone (tetracyclone) is an excellent diene trap in Diels-

Alder reactions.02 1,2,3,4-Tetraphenylnaphthalene (70%) was obtained by Cadogan

when using tetracyclone to trap benzyne in his original report. In the case of AF4-yne,

83% yield of adduct was obtained (Figure 3-6).


Figure 3-6 Chemical shifts of tetracyclone with AF4-yne product









The assignment of the protons on the phenyl rings of this adduct was accomplished

based on the H1-H1 couplings seen in the DQCOSY spectrum. Both phenyl rings

displayed non-equivalence of the ortho and meta positions, indicative of restricted

rotation. A quick variable temperature run showed that the pairs 6.80 7.07 coalesced at

50 60 C, while the protons on the other ring displayed no broadening at 60 OC. The

assignment of the carbons on the phenyl ring, as well as of those adjacent to the ipso

positions was done on the basis of the H1-C13 couplings, one-bond and long-range, seen

in the GHMQC and GHMBC spectra, correspondingly. The NOESY spectrum at room

temperature displayed a nOe between 7.45 and 7.30, which identified the protons on the

same side of the paracyclophane. The assignment of the rest of the carbons followed from

the H1-C13 couplings. The only other non-trivial nOe in the NOESY spectrum was 6.93-

7.35. A ROESY spectrum was then run at -20 OC, temperature at which all protons

displayed sharp signals. The nOe between 7.30 and 6.80 (chemical shifts at room

temperature) allowed the assignment of the faster rotating phenyl ring to position 1 on the

naphthalene, and of the proton at 6.80 to the side exo to the cyclophane moiety. The nOe

between 7.35 and 6.93 agrees with a MM calculation in Perch, in which the phenyls in

positions 2 and 3 are on the side of the naphthalene ring towards the cyclophane, while

the phenyls in positions 1 and 4 are on the opposite side. NOe's of 7.07 with both 7.35

and 6.03, in conditions in which 6.80 does not display any nOe with protons on the other

phenyl ring, agree with this model.

3.2.5 Norbornadiene Reactions

As described in Chapter 2, the AF4-yne generated from IAF4 under Cram

conditions, gave major [2+2+2] adducts instead of the major [2+2] products that were

observed by Heaney98 and Noble99 in their studies of the reactions of halogenated









benzyne with norbornadiene. Tabushi, et al. also reported the predominant [2+2]

cycloaddition products in the reactions of norbornadiene and quadricyclane with benzyne,

ratio of 73/27 and 67/33, respectively, compared to [2+2+2] products.104 In the case of

AF4-yne as generated from 4-(N-nitroso)- AF4 acetamide (Cadogan method),103 the

major products formed with norbornadiene were the [2+2+2] products as listed in Table

3-1, but the preference was not so strong as under Cram conditions.

Table 3-1 [2+2+2] to [2+2] products ratio of norbornadiene with AF4-yne
method solvent Temperature( C )a Ratio(15la: 15b:16a: 16b)b

Cram Butyl ether 142(160) 62:27:3:8

Cram norbornadiene 90(110) 74:12:10:4

Cadogan Butyl ether 90(110) 39:21:21:19

a. Temperature in the parenthesis is the oil bath value. b. see Chapter 2

3.2.6 Reaction with 1,3,5-Cycloheptatriene

The reaction of cycloheptatriene with benzyne provided another illustrative

example of novel benzyne chemistry. Initially, Tabushi et al.104 claimed that

cycloheptatriene underwent a [2+6] cycloaddition along with ene reaction (approximately

1:1 ratio) in its reaction with benzyne. It turned out that the product was a [2+2] instead

of a [2+6] cycloadduct, as reported by Lombardo105, 106 and Crews107shortly thereafter,

with an overall yield in the reaction was about 25%. [2+4] Cycloadducts were not

observed in these investigations. Tropone reacted with benzyne to give a predominant

[2+4] cycloadduct under the same conditions.106 The rationale is that tropone has a planar

structure while that of cycloheptatriene is not planar.

Surprisingly, AF4-yne generated from Cadogan's method didn't yield any [2+2]

cycloadduct. All observed products were derived from an initial ene reaction (yields of









61%). The primary ene product then reacted with another AF4-yne, apparently via the

norcaradiene tautomer to give bis-AF4 adducts endo- 8a and exo-8b (1:1) in 38% yields

as showed in Figure 3-7. In contrast, the AF4-yne as generated from Cram's method gave

only reduced AF4 (31%) plus the t-butoxide ion adduct (51%) in the reaction with

cycloheptatriene. Neither [2+2], [2+4] nor ene reactions were observed.

Proton and carbon chemical shifts of the products are illustrated below. The

sequence of protons in the contiguous coupling network of [4.1.0]-bicyclohepta-3-ene

moiety was revealed by the DQCOSY experiment. The carbons to which these protons

are bound were identified in the GHMQC spectrum. Proton-carbon couplings of ca. 165-

175 Hz confirmed the methines of the cyclopropyl ring. The three carbons on the AF4

frames to which the [4.1.0]-bicyclohepta-3-ene moiety is attached (at ca. 140-145 ppm)

have been identified by their cross-peaks in the GHMBC spectra to protons two or three

bonds away. The carbons adjacent to them couple with the protons three bonds away, e.g.,

in the case of 8a, 2.54 couples with 126.5 and 131.4, 129.2 couples with 4.89, and 128.5

couples with 4.74. Three of these carbons, at 129.2, 128.5 and 131.4 are split as a triplet

of ca. 30-35 Hz by the two fluorines two bonds away. The remaining protons and carbons

on the para-phenylene moieties to which the [4.1.0]-bicyclohepta-3-ene moiety is

attached were assigned on the basis of the couplings between protons and carbons three

bonds away. The DQCOSY spectrum confirmed the large coupling between protons

which are ortho and the small couplings between protons which are meta.

The configuration of compounds 8a and 8b was established by nOe's. In both 8a

and 8b, the cyclopropyl protons adjacent to the AF4 display an nOe to the alkene protons






























6.17
8a


130. 129.1 11b. 2 7.01
6.49 F F 7.31 128.4
8 F 144.1 21430 125.4
16 36.6 2.45 130.9 126.1 129
4.74 6.94 129.
26.4 25.0 7.04 7.10
0.94 140.9 125.5 133.9

125.8\ 125.0 F F
6.11 6.84 117.6
133.9
8b
F117.4 F


017.6



727.27
128.2 133.3- 7.11 F- F



71127.5 7.09
134.0 --- 128.2 7

F ~~ 75 7 .1 645 F F 09 6 5.47
7.16 7" 5.50 125.526120.1
6.99 126.7 130. 18.4F162 1255 F F129 120.1
26.8 6.70 6.9837
12. 129.4 26 62.426
131.2 142.9 39.1 19142.6 139.3

F 117.9 F .18 130.0 F F 709 122.1
120.2 6.62 133.4 5.49
4.58 123.2 6.53 125.0
6.04 6.24
9a 9b
Figure 3-7 Chemical shifts of cycloheptatriene products 8 and 9

(2.54 with 6.17 and 6.23; 2.45 with 6.49 and 6.55) while the other cyclopropyl protons do









not, therefore the configuration of the [4.1.0]-bicyclohepta-3-ene moiety is endo in

bothcompounds. In 8a, the cyclopropyl protons at 1.67 and 1.97 display an nOe with two

aromatic protons at 6.89 and 6.94, while in 8b the alkene protons at 6.49 and 6.55 display

nOe's with the aromatic protons at 6.84 and 6.85, indicating that the addition of the

[4.1.0]-bicyclohepta-1,3-diene yielded the endo product for 8a and the exo product for 8b.

The relative size of these nOe's allowed the assignment of the aromatic protons, i.e., the

nOe of 1.67 with 6.89 was larger than the nOe of 1.67 with 6.94.

The use of nOe's in the assignment of the configuration of the AF4 unit bound to

the cyclopropyl was based on the fact that the cyclopropyl proton ac to the AF4 (2.54 in

8a) is approximately in the plane of the para-phenylene and is facing the nearest CF2.

This is the geometry found by a conformational search using MM2 in Hyperchem, and

confirmed by the nOe's displayed by the products of the reaction of the AF4 arene with

cyclopentene and with cyclohexene [page 59]. In compound 8a, 1.97 displays nOe's with

two aromatic protons at 7.08 and 7.40, while 1.67 does not, therefore the otherpara-

phenylene ring of the AF4 moiety bound to the cyclopropyl ring is on the same side of

this ring as 1.97. Of 7.40 and 7.08, only the former displays an nOe with 2.54, therefore

they are syn. Similar nOes' were used in the case of 8b, to assign the protons at 7.31 and

7.04.

Simple ene products 9a and 9b (2:1) as depicted in Figure 3-6 were also obtained

in 23% yield, the latter deriving from 9a via subsequent 1,5-H shift. The GIHMBC

spectrum displayed couplings for 9a between the protons at 5.50 and 4.58 and the carbon

at 142.9, and for 9b between the protons at 6.26 and 6.53 and the carbon at 142.6, which

identified the carbon on the AF4 moiety to which the cycloheptatriene moiety is









connected. Couplings between the protons and carbons of the methines at 39.1, 3.06 and

at 126.8, 7.18 identified the methine ortho to 142.9 in 9a. A similar coupling between the

proton at 7.09 and the carbon at 139.3 identified the proton ortho to 142.6 in 9b. Long-

range couplings between the protons and carbons in a meta relationship were used to

assign the chemical shifts on the AF4 moiety for 9a. In the case of the minor product 9b,

these assignments could not be made because of severe overlap with the stronger peaks of

9a.

The assignment of the protons on the cycloheptatriene moiety in 9a assumed a

geometry in which the proton at 3.06 is in the plane of thepara-phenylene and is facing

the nearest CF2. This is the geometry found by a conformational search using MM2 in

Hyperchem, and confirmed by the nOe's displayed by the products of the reaction of the

AF4 arene with cyclopentene and with cyclohexene [page 59]. Two nOe's, between 3.06

and 7.21 and between 5.50 and 7.11 allowed the assignment of the protons on the face of

the otherpara-penylene moiety of the AF4, as 7.21 being syn to 3.06. 4.58 display a nOe

with 7.18 only. The conformation of the cycloheptatriene ring in 9a is with the double

bond having 6.62 and 6.70 folded toward 3.06, as demonstrated by nOe's between 3.06

and these other two protons.

In the case of 9b, both 6.26 and 6.53 display nOe's with 7.27 and 7.09, as

expected for little preference for one orientation or the other of the cycloheptatriene

moiety. The most shielded proton at 7.27 was assigned as syn to the cycloheptatriene.

The side endo to the AF4 displayed deshielding compared to the side exo in all of the

compounds studied; therefore one can assume that the preferred conformation has the

CH2 of cycloheptatriene on the exo side of the AF4.









Normally, cycloheptatriene undergoes DA reactions with most dienophiles via its

valence tautomer, bicyclo[4.1.0]hepta-2,4-diene (norcaradiene) which is present in very

small quantities in equilibrium with cycloheptatriene.08' 109 With an extremely reactive

reagent such as benzyne, the benzyne is apparently so reactive that it reacts preferentially

with the major tautomer and there is simply too little norcaradiene present to lead to

significant product.

Why should the very reactive AF4-yne give rise to norcaradiene derived products

(8a& 8b) when benzyne itself did not? It may be that the primary ene product, 7-AF4-

substituted cycloheptatriene, has a much greater amount of its respective norcaradiene

tautomer present in equilibrium, thus allowing AF4-yne to react with this tautomer in the

preferred manner. Ciganek et al. found that substitutents containing 7t systems would help

the stabilization of the norcaradiene valence isomer.110 AF4 system is quite electron

deficient due to the two bridge fluorine substitutents, and importantly, AF4 moiety is

quite bulky which will force the equilibrium to the side of norcaradiene tautomer.109


HAF4 AF4 AF4-yne_ DA products 8a & 8b
(>H qAF4
H

Figure 3-8 Primary AF4-yne ene product with AF4-yne reaction to products 8a&8b

Equilibrium of cycloheptatriene with norcaradiene has been extensively studied in

1960's and 1970's. No norcaradiene valence tautomer could be detected by variable-

temperature 1H NMR even down to -150C. 111, 112 Only ca. 3% norcaradiene could be

observed for 7-carboxyl acid substituted derivative at the above temperature.113 With two

7t acceptor substitutents at 7 position, for example, CN, the norcaradiene is the more

stable form by ca. 6 kcal,110' 114 whereas that of unsubstituted cycloheptatriene is the more









stable form by ca. 11 kcal.115' 116 Adam et al.109 studied the cycloaddition of 7-substituted

cycloheptatriene with singlet oxygen and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD),

which is a very dienophilic reagent. He found that the product ratio with singlet oxygen

follow the order CHO C CO2Me C CN > ph > H > MeO, the norcaradiene [2+4] adduct

increase from the left to right, being exclusively norcaradiene adduct for MeO and

exclusively cyclohetpatriene adduct for CHO, CO2Me and CN. For H mainly the former

and for ph mainly the later are formed. In contrast, only the norcaradiene [2+4] adduct

was produced for PTAD for all substituents. H electron acceptor such as CN, CO2Me and

CHO, stabilize the cyclopropane ring by decreasing the antibonding C1-C6 electron

density, while the effect is reversed for 7t donor MeO. His rationale for the abnormal

product for PTAD is that the cycloaddition activation energy for cycloheptatriene is much

high than that of norcaradiene, 17-20 kcal/mol, lie well beyond the equilibrium activation

energy, 2-12kcal/mol. Comparing with the singlet oxygen, PTAD is much more slower

and more selective with in its dienophilic reaction with cycloheptatriene.

Similarly, AF4-yne is quite bulky and reactive intermediate, the cycloaddition

activation energy must be very high for cycloheptatriene due to the steric issue, while that

for norcaradiene is much lower and faster reaction. On the other hand, AF4 moiety is

electron deficient 7n acceptor, the equilibrium of 7-AF4-cycloheptatriene would favor the

7-AF4-norcaradiene, which in turn would increase the reaction rate of norcaradiene with

AF4-yne.

3.3 Mechanistic Study of AF4-yne

The parent benzyne and eventually all 1,2-arynes have singlet ground state, with o-

benzyne itself having a singlet-triplet energy gap of 37.5 kcalmol1.57'17 Since arynes are









simple strained alkynes, the Woodward-Hoffmann rules do not permit a concerted

superafacial (S) 2S+2S thermal cycloaddition. On the other hand, [2+4] cycloadditions

should be concerted, stereospecific reactions. Dienes generally undergo [2+4]

cycloadditions with arynes, but when the diene system is sufficiently distorted from

planarity, step wise [2+2] cycloaddition with benzyne becomes energetically feasible.107

3.3.1 Base and Solvent Study

Arynes are also very reactive towards nucleophilic addition.66' 118-120 There is a

question therefore regarding why there is no t-butoxide ion adduct formed in the AF4-yne

reactions, in contrast to that Cram originally reported with his benzyne study.24 Base and

solvent effects in this AF4-yne system were investigated (Table 3-2). A striking

observation is that no DA reaction with anthracene is observed when sodium t-butoxide

is used instead of potassium t-butoxide. After refluxing in butyl ether for two hours, most

starting material remains. Sodium amide, which is a strong and commonly used base for

aryne generation,70' 121-23 also gives no anthracene adduct in butyl ether (of course, it

may be destroyed by butyl ether). Reduced product AF4 plus 5% DA products with some

starting material were observed when refluxing in t-butylbenzene for two hours in the

reaction of IAF4 with NaOtBu. In the polar solvent DMF, sodium amide simply reduces

IAF4 to AF4 in over 90% yield.

Table 3-2 Base and solvent effects in AF4-yne reaction with anthracene
Solvent Base Temperature Time Diels-Alder adduct %

(C) (min) (from the 19F spectrum)
t-butylbenzene KOBut 169 30 83
Butyl ether KOBut 142 30 82
Butyl ether NaOBut 142 120 SM
t-butylbenzene NaOBut 169 60 IAF4:AF4:DA









9.24:1:1.27
Butyl ether NaNH2 142 120 Starting Material
t-butylbenzene NaNH2 169 270 IAF4:AF4:DA
2.70:1.21:1
Butyl ether NaHMDS Room 18h Starting material
DMF NaNH2 Room 18h AF4 (90%)
DMF: dimethylformamide; HMDS: 1,1,1,3,3,3-hexamethyldisilazane; DA: Diels-
Alder adduct.

Why is the same base with different cations so different in the aryne generation?

Sodium t-butoxide works better than sodium amide and potassium t-butoxide in the

formation of t-butyl hypoiodite in cyclohexane by Wirth.124 The solubility played an

important role in that reaction system. Thus, the solubility of sodium and potassium t-

butoxide in butyl ether was examined (Table 3-3).

Table 3-3 Base solubility in butyl ether solvent
Base Refluxing time solubility
NaO tBu (0.1132g) 5 min in 14 ml Clear solution
KOtBu (0.1123g) 30 min in 64 ml Most solid remains
It is obvious that sodium t-butoxide has much better solubility in butyl ether than

potassium t-butoxide does. A heterogeneous reaction system makes the base stronger!

The dehydrogenation probably occurs on the surface of the strong base. The lack of

reaction with sodium amide might be due to its limited surface area (pellets). In the

reaction of IAF4 with sodium amide in t-butylbenzene, only 20% DA product was

observed, whereas 100% of the starting material is recovered in butyl ether (Table 3-3).

3.3.2 The Different Selectivity of the Two Methods

Why does the same aryne generated by different methods have such a huge

difference in reactivity towards the same substrates? AF4-yne generated via the Cadogan

method gave ene products in the presence of alkene, whereas only reduced AF4 was









observed from the AF4-yne generated by the Cram method for the same type of reaction.

The selectivity of arynes towards different substrates was examined first.

Anthracene is such an excellent diene trap that the difference of speed of aryne

generation may not be discerned between two methods. Therefore, naphthalene and

benzene were first used as the diene trap in the competition experiments between

Cadogan and Cram methods. Two methods' selectivity towards benzene and naphthalene

are listed in Table 3-4. Both methods show that naphthalene reacts much faster as the

benzyne trap, which is consistent with earlier reports.87 88 The selectivities of naphthalene

to benzene in Cadogan and Cram method are 512:1 and 285:1, respectively.

Anthracene is the one of the most reactive diene trap in benzyne chemistry, but its

actual selectivity versus benzene and naphthalene was not available. The competition

between anthracene and naphthalene in DA reaction was carried out under Cram

conditions, and the result was summarized in Table 3-5. In order to compare the result

between Cram and Cadogan methods, some reactions were carried out in butyl ether at

110OC, which are the typical conditions for Cadogan method.

Table 3-4 Competition reactions of naphthalene to benzene
method substrate Time Product selectivity
(min) ratio
Cram Ben:Naph=l:l 30 Naph adduct 100%
Cram Ben:Naph=112:1 180 Naph:Ben Naph:Ben=307:1
74:26
Cram Ben:naph=169:1 180 Naph:Ben Naph:Ben=287:1
63:37
Cram Ben:naph=449:1 180 Naph:Ben Naph:Ben=260:1
37:63
Cadogan Ben:naph=63:1 Over Naph:Ben Naph:Ben=332:1
night 84:16
Cadogan Ben:naph=215:1 Over Naph:Ben Naph:Ben=688:1
night 76:24
Cadogan Ben:naph=493:1 Over Naph:Ben Naph:Ben=516:1
night 54:46























Reactions were run at 110 C in butyl ether. Naph=naphthalene;
DA=Diels-Adler.
Table 3-5 Selectivity in Diels-Alder reaction under Cram conditions


Ben=benzene;


substrates Temp (C) DA adduct ratio selectivity

Anth:Naph= 1:10 142(reflux) Anth:Naph=73:27 Anth:Naph=26:1
Anth:Naph=l : 10 110 Anth:Naph=75:25 Anth:Naph=30:1
Naph:Ben=1:50 110 Naph:Ben=80:20 Naph:Ben=200:1


When temperature is lower, AF4-yne has better selectivity to anthracene over

naphthalene, 30/1 at 110C compared to 26/1 at 142C. While the selectivity to

naphthalene over benzene is 200/1 under Cram conditions compared to 512/1 under

Cadogan conditions, which shows that AF4-yne generated under Cadogan conditions has

better selectivity. We can deduce that selectivity to anthracene over benzene is 6000/1

under Cram conditions.

Benzene is stable and the worst diene trap in benzyne DA reactions,87 which is also

obvious from the competition results above. The competition reaction of benzene with 1-

octene (Table 3-6) gave only ene product under Cadogan conditions. When the same

reaction was carried out under Cram conditions, reduced AF4 was the sole product with a

large excess of 1-octene. t-Butoxide ion addition product was the major product along


Cram 1,4-dimethylnaph 20 Endo:exo Adduct on non
80:20 substituted ring
Cadogan 1,4-dimethylnaph Over Endo:exo Adduct on non
night 65:35 substituted ring
Cram 2,3-dimethylnaph 30 Endo Adduct on
substituted ring
Cadogan 2,3-diemthylnaph Over endo Adduct on
night substituted ring
Cram 2-methoxynaph 30 3 adducts endo Adduct on
major substituted ring
Cadogan 2-methoxynaph Over different Adduct on
night product substituted ring









with reduced AF4 (former: AF4=1.5:1) if only 1.2 equivalents of 1-octene is used.

Normally, t-butoxide adduct is not observed under Cram conditions.

Table 3-6 Competition reactions of benzene to 1-octene
method substrate Time(min) results
Cram Ben: -octene=1:1 5 hrs AF4:DA:other=32:2:46
Cram Ben:1-octene=1:4 Shrs AF4:DA:other=76:4:20
Cram Ben:1-octene=1:45 5 hrs AF4
Cadogan Ben: 1-octene=1:1 Over night Ene product

Reactions were run at 110 "C in butyl ether. Ben=benzene; DA=Diels-Adler;
other=t-butoxide ion adduct.

3.3.3 The Selectivity of AF4-yne Toward Diels-Alder and Ene reaction

Benzene is apparently not fast enough to capture all the AF4-yne when it is formed

under Cram condition, thus, the above results could not provide the right information on

the degree of aryne formation. Thus, anthracene was used as the diene trap in competition

reactions with 1-octene. We assume that all the arynes were trapped by anthracene as

soon as arynes were formed. The result is showed in Table 3-7.

Table 3-7 Competition reaction of anthracene with 1-octene in butyl ether for 5 hours at
110C under Cram condition
Ratio(anthracene/1-octene) Results (DA products/AF4)
1:1 100
1:10 82:18
1:40 55:45
1:100 30:70

The data shows explicitly that aryne was formed even with 100 equivalents excess

of 1-octene. So why was no ene reaction observed under Cram condition? The reduction

rate of IAF4 to AF4 increases as the concentration of 1-octene increases. But this is not

the case in norbornadiene reactions. The reactions of other alkenes with AF4-yne under

Cram condition were summarized in Table 3-8. The amount of reduced AF4 increases as









the amount of olefins increases, which means that olefin does have some effect in the

reduction of AF4-yne.

Table 3-8 Reaction of AF4-yne with olefins in butyl ether
Method Substrate (equiv.) Conditions Results
Cadogan 1-octene(2) 110OC 83% ene products

Cram 1-octene(2) 110OC 3h 26%AF4 + 74% other

Cram 1-octene(10) 110C 3h 64%AF4 + 36% other

Cram Cycloheptatriene(4) 120OC 5h 31%AF4 + 50% other"

Cram Pure 1-octene Reflux 3h >90% AF4
Cadogan Cyclohexene(2) 110 C 55% ene products

Cram 1-hexene(2) 110C 3h 22%AF4 + 76% other"

Cram 1-hexene(40) 110 C 6h >90%AF4

Cram t-butylethylene (2) 110C 5h 42% AF4 + 57% other

Cram t-butylethylene(100) 110C 5h IAF4:AF4:DA
anthracene(l) 64:11:25
a: t-butoxide adduct; b: 2+2 cycloadduct

Is AF4-yne formed under Cadogan conditions? Ene product was the only

observable one when benzene and 1-octene were presented in a 1:1 ratio (Table 3-6). Is

there any special selectivity toward ene reaction under Cadogan condition? Competition

of ene with DA reaction was investigated and summarized in Table 3-9.

Table 3-9 The AF4-yne selectivity of DA over Ene reaction under Cadogan conditions (3
h at 110 C in butyl ether)
substrates Products ratio (DA:Ene) Selectivity (DA/ene)

Benzene: 1-octene 1:1 Ene --

Benzene: 1-octene 40:1 19:81 1/139

Anthracene: 1-octene 1:10 96:4 197/1









Naphthalene: 1-octene 1:1 69:31 2/1


The DA reaction of anthracene with AF4-yne is 197 times faster than ene reaction

of AF4-yne with 1-octene, while that is just 2 times faster with naphthalene as diene trap

in competition with ene reaction. It is very clear that benzene is much poorer diene trap

than anthracene and naphthalene. Anthracene is 2.7*104 faster in DA reaction than

benzene, which is consistent with the very poor yields for the DA reaction of benzene

with some benzynes.

Looking back at Table 3-4 and Table 3-5, we found that anthracene was more

reactive than naphthalene and benzene by 30 times and 6000 times respectively under

Cram conditions. The same relative reactivities are 98 and 2.7*104 toward naphthalene

and benzene respectively under Cadogan conditions. The reason for the significant

difference is not clear. To keep in mind that the former reactivity measurement was based

on competition of DA reactions, whereas the latter one was based on the DA vs ene

reactions.

3.3.4 t-Butoxide Ion Adduct

One of the control experiments of IAF with KOtBu and anthracene was carried out

in butyl ether, with 100 equivalents of t-butylethylene added to the reaction mixture.

After stirring at 110"C for 6 hours, 11% reduced AF4 and 25% anthracene adduct were

obtained with 64% starting material remaining. The slower rate may due to the lower

boiling point of t-butylethylene (bp 41 C). When the alkene concentration was low, t-

butoxide ion adduct was observed predominantly and this product decreases as the olefin

concentration increases. Table 3-10 summarizes the results where the t-butoxide ion









adduct was observed. Cycloheptatriene with AF4-yne under Cram's conditions give 50%

t-butoxide ion adduct with 31% AF4, acting as a normal alkene in this case.

Table 3-10 Summary of t-butoxide adduct under Cram's conditions
reaction Yield of t-butoxide adduct (5)

Benzene+1-octene (1:1) 46

Benzene+1-octene (4:4) 20

1-octene (2) 74

1-octene(10) 36

1-hexene(2) 76

Cycloheptatriene(4) 50


50% of t-Butoxide ion adduct was obtained with 31% AF4 in the reaction of

cycloheptatriene with AF4-yne generated under Cram conditions, whereas 61% ene

reaction product was observed under Cadogan conditions. 1-Hexene works the same way

as 1-octene does to give 76% t-butoxide ion adduct if 2 equivalents 1-hexene is used.

3.3.5 Mechanism

What is the difference between these olefins? Norbomadiene, a reactive olefin, gave

mainly [2+2+2] cycloadducts under Cram's conditions, whereas other alkenes do not

give adducts. Was AF4-yne reduced by alkenes through electron transfer mechanism?

The ionization potential of some alkenes is listed in Table 3-11. Electrons in the

norbomadiene double bonds are delocalized due to the strain induced overlap. The bond

order for the carbon-carbon bonds calculated by Brunger et al is 1.90 for the double

bonds and 0.924 for the single bonds in norbornadiene, respectively.125 The ionization

potential of norbornadiene is 8.69 -8.73 eV, which is nearly 1 eV lower that of 1-octene.









The energy level of electrons becomes higher as the substitutents on the double bond

increase. It is interesting that the ionization potential ofbenzyne is 9.75 eV, much higher

than most olefins. IAF4 is reduced by 1-octene but not by norbornadiene (chapter 2), thus,

the reduction of AF4-yne by electron transfer from the olefin can be excluded from

consideration.

Iodide is a good leaving group and the fluorinated bridges provide the strong

electron-withdrawing groups in the AF4 molecule. Therefore it should be possible to

reduce IAF4 to AF4 directly. It has been found that alkyl halides undergo substitution

reactions by the electron transfer, or SRN1 mechanism.127, 128 In the study of

perfluoroalkyl iodides, which can not undergo SN1 or SN2 substitution with nucleophiles,

Chen at al found that perfluoroalkyl iodide can be substituted by a SRN1 type reaction

very easily.129, 130 Perfluoroalkyl halides can also be reduced by a SRN1 mechanism.131

Iodide ion was released in 68% yield after 30 min in the reaction of iodobenzene with

potassium pinacolone enolate in the dark, while bromo-derivative was much less reactive

under the same conditions.132 Costentin at al reported thermal type SRN1 reaction with 4-

nitrocumyl chloride and 2-nitropropanate ion, which underwent either concerted or

stepwise dissociation of C-Cl bond depending on the properties of the nucleophile.133

Table 3-11 Ionization potential of alkenes126
alkene ionization potential* (eV)

norbornadiene 8.69-8.73 (PE)

propene 9.70-10.2(PE), 9.73(PI)

1-butene 9.62-9.77(PE), 9.59(PI)

cyclohexene 9.11-9.12(PE), 8.94(PI)









t-butylethylene 9.45(PE)

1-octene 9.60(PE), 9.427(PI)

cis-2-octene 9.10(PE), 8.913(PI)

benzene 9.2-9.25(PE), 9.20-9.27(EI)

fluorobenzene 9.11-9.37(PE), 9.75(PI)

a,a,a-trifluorobenzene 9.68(PE)

benzyne(1,3-cyclohexadien-5-yne) 9.75(EI)

*PE, photoelectron spectroscopy; PI, photoionization; El, electron impact.

Potassium t-butoxide could act as electron donor and could potentially reduce IAF4

via a SRN1 mechanism (Figure 3-9). After the first electron transfer from the base, the

AF4 radical could be obtained through dissociation of IAF4 radical anion. The radical

could either accept another electron to become an anion and be protonated to form AF4

from there, or it could react with t-butoxide ion to get another radical anion (SRNI

reaction). The latter radical anion could then transfer an electron to another IAF4 and

produce t-butoxide ion adduct and close the free radical chain circle. The t-butoxide ion

adduct was observed in the reactions where the olefin concentration was not high (Table

3-9). When the concentration of alkenes was high (>10eqiv.), the reduction from the AF4

radical directly must be predominant process.










F FF FF
F F
S F I (CH3)3COK (5) H

butyl ether
F F 1100C, 3h F F
FF FF


(CH3)3CO electron transfer RH


F F F F F F
F F F
p ET


F F
FF F F F F
FF FF

S(CH3)3CO0


FF FF FF -
F F[
IAF4 \ \

S ~OC(CH3)3 OC(CH3)3

FFF F F F F
Figure 3-9 SRN1 reduction of IAF4 to AF4

From Table 3-7, the AF4-yne was formed during the reaction process even with 100

equivalents of 1-octene. Thus, AF4-yne must be generated with or without any diene trap

inside. If there was no substrate, reduced AF4 was observed with over 90% yields in the

reaction of IAF4 with KOtBu in butyl ether (Table 3-7). Therefore, a reduction

mechanism was proposed depending on the information above (Figure 3-10). After the

first electron transfer, radical anion was formed, which would grab proton from the

surrounding to generate the AF4 radical. The AF4 radical could be further reduced by

another electron transfer or attacked by t-butoxide ion to produce another radical anion

and close the mechanism circle. Since no t-butoxide ion adduct was observed in the










absence of olefin, the AF4 radical was reduced by second electron transfer to produce

AF4.


+ 1-octene










electron transfer

(CH3)3CO0


(CH3)3COK (5)

butyl ether
1100C, 3h


F F
F F




F F
FF


RH


RH


F F





F F
ETFF

ET


(CH3)3CO


)C(CH3)3


electron


F FE

~ ~ H
I I OC(CH3)3
F~ 'L ~\f~~I -


F' \ / F/\ / F
FF FF

Figure 3-10 Reduction mechanism of IAF to AF4 in the presence of olefin

Olefin in the reaction mixture may act as phase transfer reagent toward t-butoxide

ion to increase the solubility of t-butoxide ion in butyl ether by forming a complex

(Figure 3-11) which would make the t-butoxide ion attack on the AF4 radical more

feasible to generate the t-butoxide ion adduct. When the concentration of olefin became

much higher, solution became electron rich and olefin accelerated the electron transfer

process.


F FF


F F

F F
FF











0,
0 "'KO



Figure 3-11 Olefin with KOtBu complex

3.3.6 Isotopic Labeling Experiments

Isotopic labeling experiments were carried out to examine the mechanism. The

reaction of IAF4 with KOtBu was much slower in the presence of equal amount of t-butyl

alcohol (Table 3-12). Alcohol increased the solubility of KOtBu and made the base

weaker. The NMR spectrum found deuterium incorporation in the reduced product of

IAF4 with KOBut/DOtBu without a diene trap. The MS also showed fragment of

176(100), 177(53), 352(14), and 353(14), which meant about half of the reduced AF4

(38%) was deuterated. Deuterium exchange was also observed in this reaction.

Recovered starting material IAF4 (22%) showed a peak at 479(5), 478(3), the isotopic

ratio was much higher than that in pure IAF4 with MS peaks of 479(6) and 478(60). As

expected, 44% DA products were observed in the presence of 1 equivalent of anthracene

in the above reaction. AF4 was obtained in 52% and 40% yields in the reactions of AF4-

yne with acetonitrile and N,N-dimthylformamide (DMF) as solvents, respectively.

Dideuterated AF4 was observed in the reaction of IAF4 with KOtBu in CD3CN in a ratio

1:1 with respect to the mono-deuterated AF4. The MS spectrum showed peaks at 354(19),

353(31), 353(12), 352(9) and fragments 178(54), 177(54), 177(35), 176(100) respectively,

which meant that half of the AF4 obtained the second proton from the surrounding or

moist during the workup. The formation of dideuterium substituted AF4 may indicate









that the AF4-yne was formed and then reduced during the reaction course. The peaks of

353(12) and 177(35) came from the natural 13C isotope of carbon.

Table 3-12 IAF4 reduced to AF4 in refluxing butyl ethera
Reaction Time Result (AF4)
(min)
IAF4 + KOBut (5)b 30 >90%
IAF4 + anthracene+ KOBut (5) + HOBut (5) 300 31% + 44% DA + other
products
IAF4 + KOBut (5) + HOBut (5) 300 47% + other products
IAF4 + KOBut (5) + DOBut (5) 300 50.6% +other products
IAF4 + KOBut (5) + acetonitrile 30 AF4 (33%)+ ring opening
IAF4 + KOBut (5) + DMF 30 AF4 (40%) + unknown
a Default solvent unless mentioned separately; b In the parenthesis is the equivalent
used; c the other products are ether adduct to AF4-yne. DA: Diels-Alder adduct.

The reaction of IAF4 with KOtBu in 1,1,1',1'-tetradeuterobutyl ether was also

investigated and was much slower than the same reaction in the non deuterated ether.

After refluxing overnight, most starting material remained. This may due to the 1,1,1',1'-

tetradeuterobutyl ether is not pure enough or some alcohol is inside, which would make

reaction much slower.

3.3.7 Reactions in the Presence of Electron Trap Reagents

p-Dinitrobenzene (p-DNB) was used as electron trap reagents for verifying the SRN1

mechanism,132, 134 andp-DNB suppressed the electron transfer process in the radical

nucleophilic substitution of perfluoroalkyl iodide.130 The additive experiments were

carried out to test our proposal, and results are listed in Table 3-13.









Table 3-13 Additive effect on the reduction of AF4-yne with 1-octene under Cram
conditions at 110C for 3 h
Additive Results (ratio)

AF4:IAF4:t-butoxide adduct

p-DNB (2) 45:55:0

p-DNB (0.2) 31:0:69

Nitrobenzene (4) 38:62:0

Nitrobenzene (2) 54:25:21

Nitrobenzene (1) 62:14:24

Nitrobenzene (0.5) 59:0:41


However, no ene product is observed by adding eitherp-DNB or nitrobenzene.

Nevertheless, these two additives did have effect on the reaction of IAF4; the reaction

rate is much slower with 1 equivalent of nitrobenzene, 14% IAF4 remains after stirring at

110"C for 3 h in butyl ether. The amount of starting material increased as the amount of

nitrobenzene orp-DNB increased. 45% Reduced AF4 was detected by 19F NMR from the

crude reaction mixture along with 55% of starting material after 3 h at 110C with 2

equivalents ofp-DNB, while that was 25% with 2 equivalents of nitrobenzene. The t-

butoxide ion product decreased as the amount of additive increased. There was no

difference compared to the reaction of IAF4 with 1-octene under Cram conditions

without any additive (Table 3-6) if only 0.2 equivalent ofp-DNB or 0.5 equivalents of

nitrobenzene was added. In Scamehorn's study of halobenzene reactions,132 p-DNB gave

substantial electron trapping effect, while the nitrobenzene only had limited inhibition at

the beginning, and then was followed by an increasing reaction rate. It seems that

nitrobenzene is not as effective asp-DNB is, but they both work the same way in this









system. Excess ofp-DNB or nitrobenzene might change the entire reaction course due to

nitro- group strong electron withdrawing capability, while it was consumed quickly by

the t-butoxide ion and had limited impact with limited amount.

Table 3-14 Additive effect on the reaction of AF4-yne with anthracene under Cram
conditions at 110C for 3 h
Additive Result (AF4:IAF4:DA adduct)

Nitrobenzene (1) 5:0:95

Nitrobenzene (4) 11:5:84

Nitrobenzene (4) + 1-ocetne (2) 10:30:60

p-DNB (2) +1-octene (2) 38:17:45

Similarly, the addictive effects on the DA reaction were carried out with anthracene

as substrate (Table 3-14). Large amount of nitrobenzene (4 equiv.) would increase the

amount of reduced AF4 to 11% along with 5% starting material from 5% AF4 and no

starting material in the presence of 1 equivalent of nitrobenzene. The addition of 1-octene

did have effect on the formation of AF4-yne. 30% of starting material remained in the

same reaction with of 2 equiv. of 1-octene inside and the DA adduct decreased to 60%

from 80% in the absence of 1-octene. While replacing the nitrobenzene with p-DNB, the

amount of AF4 simply increased to 38%, which meant that p-DNB had more effect on

the reduction of IAF4 or AF4-yne to AF4.

3.4 Conclusion

A different method of generating AF4-yne in situ from N-(nitroso)-AF4 acetamide

was discussed (Cadogan method), which gave the same results as Cram method in DA

reactions, but a totally different outcome in the reactions with alkenes. Unusual ene

reaction preference was observed in the reaction of AF4-yne generated by Cadogan