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Synthesis and chemistry of 3,4,7-metheno-3H-cyclopentaApentalenes (bisesquinanes)

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Synthesis and chemistry of 3,4,7-metheno-3H-cyclopentaApentalenes (bisesquinanes)
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Griggs, Billy Glynn, 1953-
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xi, 139 leaves : ill. ; 28 cm.

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Subjects / Keywords:
Adducts ( jstor )
Alcohols ( jstor )
Bond angles ( jstor )
Flasks ( jstor )
Ions ( jstor )
Isomers ( jstor )
Ketones ( jstor )
Mass spectra ( jstor )
Protons ( jstor )
Solvents ( jstor )
Bisesquinene ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Methoxybisesquinene ( lcsh )
Polycyclic compounds ( lcsh )
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bibliography ( marcgt )
non-fiction ( marcgt )

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Thesis:
Thesis (Ph. D.)--University of Florida, 1985.
Bibliography:
Bibliography: leaves 135-138.
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Billy Glynn Griggs, Jr.

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SYNTHESIS AND CHEMISTRY OF
3,4,7-METIIENO-3H-CYCLOPENTA[A]PENTALENES
(BISESQUINANES)










BY

BILLY GLYNN GRIGGS, JR.


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


1985




SYNTHESIS AND CHEMISTRY OF
3,4,7-METHENO-3H-CYCLOPENTA [ A ] PENTALENES
(BISESQUINANES)
BY
BILLY GLYNN GRIGGS, JR.
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
1985


IN MEMORY OF MY GRANDFATHER
who spent 40 years as a high school
teacher of chemistry, math and physics
and instilled in me a love of science


ACKNOWLEDGEMENTS
The author would like to express his gratitude to
Professor M. A. Battiste for his guidance throughout the course of this
work; his willingness to be interrupted to discuss new results or just to
chat was a joy. In his role as academic advisor, Dr. Battiste has helped
the author develop a sense of independence and maturity by knowing when
to offer help and when to leave him time to solve his own problems.
Special thanks are due to all of the author's friends who have
contributed a vital service of babysitting for the past few weeks.
Without their generous support, this manuscript v/ould never have been
completed.
Finally, to the author's typist and helpmate he says your loving
support, understanding of all the late nights in the lab, and eagerness
to help is appreciated beyond description. Your ability to take
everything in stride (almost, anyway) and maintain a semblance of order
in our household has qualified you as a Proverbs 31 woman. "An excellent
wife, who can find? For her worth is far above jewels. The heart of her
husband trusts in her, and he will have no lack of gain."
iii


TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
LIST OF TABLES viii
LIST OF FIGURES ix
ABSTRACT x
CHAPTER ONE INTRODUCTION 1
CHAPTER TWO SYNTHESIS OF METHOXYBISESQUINENE 7
Synthetic Strategy 7
Preparation of 7,7-Dimethoxynorbornene (30). 7
Preparation of 5-Trimethylsilylcyclopenta-
diene (28) 8
Reaction of 7,7,Diraethoxynorbornene with
Trimethylsilylcyclopentadiene 10
Structure Determination 11
Nuclear Magnetic Resonance 11
Mass Spectra 17
Mechanism 18
Improved Isolation of _2(3 from Isomer Mixture 19
CHAPTER THREE REACTIVITY AND REARRANGEMENTS OF BISESOUINENE. ... 22
Acid Catalyzed Rearrangements in Methoxybises-
quinene 23
Addition Reactions of the Double Bond 25
Preparation of Acid Rearrangement Products ... 28
Results of Acid Addition to the Double Bond of
Methoxybisesquinene (26) 30
Conclusions 36
IV


Page
CHAPTER FOUR STRAIN AND STRUCTURAL EFFECTS IN THE BESESQUINANE
SYSTEM 37
Strain Energy 37
MM2 Calculations 37
Homoketonization 41
Bisesquinane Structure: Calculated and X-Ray. 47
Bond Lengths 47
Bond Angles 51
13
C-H Spin-Spin Coupling and Angle Strain. 55
Interplanar Angles 56
Diels-Alder Reactivity of Bisesquinene:
Adduct Stereochemistry 58
Preparation of Adducts 61
Stereochemistry 62
Suggestions for Future Work 66
CHAPTER FIVE EXPERIMENTAL 67
General 67
Synthesis 69
Preparation of 7,7-Dimethoxynorbornene (30). 69
Preparation of 5-Trimethylsilylcyclopen-
tadiene (28) 70
Reaction of 7,7-Dimethoxynorbornene (30)
with 5-Trimethylsilylcyclopentadiene (28). 71
Method A: A1C13/CH2C12, -78?C 71
Method B: AlCl3/Et20, 0?C 71
Method C: BF3 Et20/CH2CH2, 25?C .... 72
Method D: BF3 Et20/CH2C12, 5?C 73
Spectral Data for Isolated Products from
the Reaction of 7,7-Dimethoxy-norbornene
(30) with 5-Trimethylsilylcyclopentadiene
(28) (Methods A-D) 73
7-Norbornylfulvalene (36) 73
syn-7-Methoxy-7-(1-cyclopentadienyl)-
norbornene (37a) and syn-7-methoxy-7-
(1'-cyclopentadienyl)norbornene (37b),
ca. (50:50) 75
3b-Methoxy-3a,3b,4,6a,7,7a-octahydro-
3,4,7-netheno-3H-cyclopenta?a? pen-
talene (_26) 75
v


8-Methoxy-3a,3b,4,6a,7,7a-octahydro-
3,4,7-metheno-3H-cyclopenta[a]pen-
talene (38) 76
3b-Methoxy-2,3,3a,3b,4,5,6,6a,7,7a-
octahydro-1,4,7-metheno-lH-cyclo-
penta[a]pentalene (39) 76
Preparation of 3b-Methoxy-
2,3,3a,3b,4,5,6,6a,7,7a-decahydro-l,4,7-
metheno-lH-cyclopenta[a]pentalene
(39-H2) 77
Bromination of Methoxybisesquinene (26). . 78
Preparation of trans-1,2-dibromo-3b-
methoxy-3a,3b,4,6a,7,7a-decahydro-
3.4.7-metheno-3H-cyclopenta[a]pen-
talene (26-BrQ 78
Preparation of exo,exo-l,3-dibromo-3b-
methoxy-3a,3b,4,6a,7,7a-decahydro-
2.4.7-metheno-lH-cyclopenta[a]pen-
talene (43) 79
Debromination of 26-Br^ 80
Reaction of 26_ with Trimethylsilyl Iodide
(TMS-I) 80
Preparation of exo-1,2-Epoxy-3b-methoxy-
3a,3b,4,6a,7,7a-d ecahyd ro-3,4,7-metheno-
3H-cyclopenta[a]pentalene (67) 81
Preparation of exo-l-Hydroxy-3b-methoxy-
3a,3b,4,6a,7,7a-decahydro-3,4,7-metheno-
3H-cyclopenta[a]pentalene (64-OH) 82
Preparation of exo-l-3b-Methoxy-
3a,3b,4,6a,7,7a-decahydro-3,4,7-metheno-3H-
cyclopenta[a]pentalene Acetate (64-OAc). . 83
Preparation of 11-Keto-tetracyclo-
[6.2.1. l^^.O^^]dodec-4-ene (66) 84
Preparation of anti-ll-Methoxy-tetracyclo-
[6.2.1.13,6.02,7]dodec-4-ene (72) 85
Preparation of cis,anti-4,5-Epoxy-anti-
tetracyclo[6.2.1.I3^.022]dodec-ll-
methyl Ether (73) 86
Preparation of exo-3b-Methoxy-
3a,3b,4,6a,7,7a-decahydro-2,4,7-metheno-
lH-cyclopenta[a]pentalen-3-ol (65-0H). ... 87
Preparation of 3b-Methoxy-3a,3b,4,6a,7,7a-
decahydro-3,4,7-metheno-3K-cyclopenta-
[a]pentalene (26-H^) 88
vx


Page
Preparation of 3b-Hydroxy-3a,3b,4,6a,7,7a-
decahydro-3,4,7-metheno-3H-cyclopenta-
[ajpentalene (96) 89
Preparation of Tetracyclo[7.2.1.0 .0 ]-
dodeca-l-one (98) 90
Reaction of 26. with Trifluoroacetic Acid
(TFA) 91
Preparation of Diels-Alder Adduct (103a) . 92
Treatment of Adduct 103a with TMS-1 93
Preparation of Tetrachloroketone 108 .... 93
Reaction of Tetracyclone (104) with
Methoxybisesquinene (26) to Produce
Diels-Alder Adduct 105a and Diene 106. ... 95
Spectral data for 105a 95
Spectral data for 106 96
APPENDIX 1 Nomenclature and Derivation of Trivial Name
"Bisesquinane" 97
APPENDIX 2 Selected XH and 13C NMR Spectra 101
REFERENCES 135
BIOGRAPHICAL SKETCH 139
vi i


LIST OF TABLES
Table Page
2.1 Representative Results of Reaction between Ketal 3(3
and Silane 28^ under Various Conditions 12
3.1 Acid Catalyzed Rearrangement of Methoxybisesquinene _26 . 31
4.1 MM2 Energy Calculation Results (kcal/mole) 40
4.2 Bond Lengths [] with Estimated Standard Deviations in
Parentheses for Dibromide 26-Br^ Involving Non-H Atoms . 49
O
4.3 Bond Lengths [A] forDibromide 26-Br^ Involving H Atoms . 50
4.4 Bond Angles [] with Estimated Standard Deviations in
Parentheses for Dibromide 26-Br^ 53
4.5 Bond Angles [] for Dibromide 26-8^ Involving H Atoms . 54
5.1 Method D: Fractionation by Flash Chromatography
Correlated with GC Retention Times and Area Percent. ... 74
viii


LIST OF FIGURES
Figure Page
2.1 GC of reaction mixture showing identification of isomers 13
2.2 Comparison of mass spectral fragmentation patterns for
compounds 36^ _37_, _26^ 38_ and _39 14
4.1 MM2 Calculations of strain energy. 38
4.2 INEPT 13C NMR spectrum of ketone 93 46
4.3 MM2 Calculated bond lengths for 4_, 80 and 81_ 48
4.4 Steroscopic view of the molecular structure of 26-Br^. . 47
4.5 MM2 Calculated bond angles for 4_, 80 and ^ 52
4.6 Perspective drawings of bisesquinane (4^) 55
13
4.7 C-H Coupling constants for methoxybisesquinene (26)
and related bicyclic hydrocarbons 57
4.8 Crystal structure of 26-Br^ as viewed down the
C(5) C(12) bond 58
4.9 Interplanar Angles 59
4.10 Carbonyl multiplicity 65
IX


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
SYNTHESIS AND CHEMISTRY OF
3,4,7-METHEN0-3H-CYCL0PENTA[A]PENTALENES
(BISESQUINANES)
By
Billy Glynn Griggs, Jr.
May 1985
Chairman: Dr. Merle A. Battiste
Major Department: Chemistry
An effective entry into the 3,4,7-metheno-3H-cyclopenta[a]pentalene
(bisesquinane) ring system was achieved via a novel tandem alkylation-
intramolecular [4+2] cycloaddition reaction. The addition of TMS-cyclo-
pentadiene to 5,5-dimethoxynorbornene in the presence of Lewis acid
catalysts produced 3b-methoxy-3a,3b,4,6a,7,7a-octahydro-3,4,7-metheno-3H-
cyclopenta[a]pentalene (methoxybisesquinene) as the major product in
addition to other C^H^O polycyclo-alkene isomers. A mechanism to
account for the isomeric products requires rearrangements via Tr-bond
bridging to an intermediate allyl silane cation. A simple purification
scheme via a bromination/debromination procedure was developed, thus
affording methoxybisesquinene in high purity in an overall three-step
process.
Addition reactions to methoxybisesquinene were quite facile and
under kinetic conditions gave predominantly exo addition products without
x


rearrangement. Under equilibrating conditions, Wagner-Meerwein skeletal
rearrangements occurred to produce predominantly 2,4,7-metheno-3H-cyclo-
penta[a]pentalenes (twist-methoxybisesquinenes). In no case was further
3 6 2 7
rearrangement observed to produce ll-keto-tetracyclo[6.2.1.1 .0 ]-
dodec-4-ene, the expected frangomeric cleavage product of the interme
diate twist-methoxybisesquinane cation. In fact, under acidic
conditions, this ketone was found to undergo homoconjugate addition to
produce a twist-bisesquinane diol.
The unusual chemistry of the bisesquinane system can be accounted
for by strain effects. Strain energies were calculated (MM2) for
bisesquinane and related systems to probe the effect of strain on
structure, bonding and reactivity. The calculated structural parameters
for bisesquinane are compared with those obtained from an x-ray crystal
structure of dibromomethoxybisesquinane. The two central bonds [C(10,ll)
and C(5,12)] are substantially longer than normal, implying that these
bonds are stretched as a consequence of strain. As predicted on the
basis of strain relief, homoketonization of bisesquinol produced a single
ketone. The highly compressed bridgehead bond angles of bisesquinane
contribute significantly to the strain energy and result in somewhat
larger coupling constants than related bicyclo-alkenes. The
structure of bisesquinane is unique compared to norbornane in that the
bridge methylenes are "tied back" by the central C(10)C(11) bond, which
results in a much more open exo-face. The effects of these structural
perturbations and strain on the stereochemistry of Diels-Alder reactions
with dimethoxytetrachloro-cyclopentadiene and tetracyclone were
investigated.
xi


CHAPTER ONE
INTRODUCTION
It has long been the goal of the synthetic chemist to construct
complex molecules in as few steps as necessary to perform the task at
hand. Rapid construction of multiple rings is often required in the
elaboration of complex natural and unnatural products. With this in
view, many elegant methodologies have been utilized to construct a wide
variety of polycyclic hydrocarbons.
Multiple sequence Diels-Alder cycloaddition reactions are gaining
prominence as the methods of choice for ring construction steps. One
very useful approach is the intramolecular Diels-Alder reaction, where
after the coupling of diene with a reactive ene (via a single bond
formation), the molecule is then poised to react further via succeeding
Diels-Alder coupling.
This methodology also offers the advantages of a convergent synthesis,
whereby portions of the molecule can be formed independently, and finally
brought together at a later stage in the synthetic scheme. Other
examples of multiple sequence Diels-Alder cycloaddition have been called
"Domino"^ "Timed",^ "Tandem"^ and "Diene-Transmissive"^ Diels-Alder
reactions.
1


2
An interesting variation of this theme is the Domino Diels-Alder
reaction'*' which envokes a cascading sequence of [4+2] cycloadditions.
This may be described generally as an initial intermolecular [4+2] cyclo
addition, followed by intramolecular [4+2] bonding with the newly formed
olefinic center. This process is illustrated in structures J4-3_, and
could be continued if structurally permissible.
The novel hydrocarbon skeleton "bisesquinane" (decahydro-
3,4,7-methenocyclopenta[aJpentalene, _4; see Appendix 1 for nomencla
ture discussion) has been prepared independently by Paquette and Wyvratt^
and McNeil et al.b utilizing the Domino Diels-Alder process. Their
synthesis formally requires the addition of acetylene to 9,10-dihydroful-
valene (_5) producing the intermediate 7-(5'-cyclopentadienyl)norborna-
diene (6_), which then undergoes rapid [4+2] cycloaddition to form
bisesquinadiene (_7).


3
In practice, a reactive dienophile, acetylene dicarboxylate (9),
was employed (Scheme 1.1) to produce a mixture of dicarboxylate cycload
ducts K) and H_. The isomeric mixture can be rationalized by the
approach of the dienophile (9) along coordinates a_ and Jd, respectively,
followed by the intramolecular [4+2] closure. Reduction, hydrolysis, and
oxidative decarboxylation of the minor isomer (11) afforded bisesquina-
diene (_7) in an overall yield of 7.3%.
Scheme 1.1
The research group of Paquette has recently completed the synthesis
of dodecahedrane (14), which had its genesis in the Domino Diels-Alder
reaction.^ This process allowed the multiple fusion of cyclopentane
rings conveniently and in good yield to produce the pentacyclic diester
10 which served as the "cornerstone" precursor of the elusive dodecahe
drane (14).


4
A key step in the synthesis involves cleavage of the central C-C bond,
which was facilitated by the high degree of ring strain in 10.
In view of the synthetic and theoretical interest of dodecahedrane
and its precursors, our group began exploration of alternate avenues
to polyfused cyclopentanoid systems. Synthesis of bisesquinadiene (_7) was
9
achieved by a novel approach we have termed a "tandem alkylation-[4+2]
cycloaddition." Essentially, this strategy requires the coupling of a
norbornadienyl cation (15) with a cyclopentadienyl anion (8) followed by
rapid intramolecular [4+2] cycloaddition of the intermediate 7-(5'-cyclo-
pentadienyl)norbornadiene (6_).
15 S_ 6_ _
For synthetic manipulation, this is most easily accomplished by the
in situ formation of these reactive species from 7-norbornadienyl
chloride (16) and thallium cyclopentadiene (TICp, 17) refluxed in dry
diglyme. Thus, as outlined in Scheme 1.2, bisesquinadiene (7_) was pre
pared in 8-12% yield by a convenient one-pot reaction from commercially
available starting materials.


5
Scheme 1.2
One of the major problems in this scheme is the formation of unde
sired side products. The 7-norbornadienyl cation-cyclopentadienyl anion
pair (18) can collapse at either C(7) or C(2) of the cation skeleton to pro
duce 6_ and the tricyclic hydrocarbon _19. After a series of sigmatropic
rearrangements, _19 produces a mixture of dihydro-as-indacenes (20-22).
Therefore, to improve on this methodology, one would need to increase
the charge density/localization at the 7-position of the norbornadienyl
cation (23) in order to prevent attack at C(2).
24 25
23


6
This may be accomplished by the introduction of an electron-donating
moiety at C-7 to localize the charge (e.g., _24_ => 25). The metnoxy group
has been shown to stabilize the incipient carbocation to such an extent
that participation by the double bond is relatively ineffective.^ ^
With these considerations in mind, our goal was to try to improve
this methodology to increase the yield of the reaction and to introduce
additional functionality. The target compound selected for study was
2a-methoxyoctahydro-3,4,7-methenocyclopenta[a_]pentalene (26), or more
simply, methoxybisesquinene (26). Its synthesis and reaction by-products
will be discussed in Chapter Two.
26
Methoxybisesquinene (26) offers many possibilities for mechanistic
study concerning the effect of ring strain and possible anchimeric assis
tance for thermal or acid catalyzed rearrangement. Also of interest is
the unusual reactivity of the double bond in addition reactions, and
these points will be addressed in Chapter Three.
The unusual chemistry of the bisesquinane system can be accounted
for in part due to its high ring strain. Molecular mechanics calcula
tions, an x-ray crystal structure, and a novel homoketonization experi
ment help to define the effects of this ring strain. In addition, the
facile participation of _26 as a dienophile in [4+2] cycloaddition
reactions and the questions of stereochemistry of the adducts will be
discussed in Chapter Four.


CHAPTER TWO
SYNTHESIS OF METHOXYBISESQUINENE
Synthetic Strategy
Utilizing a retrosynthetic analysis for methoxybisesquinene (26),
the application of an intramolecular Diels-Alder process preceded by. the
requisite alkylation is readily apparent.
Preparation of 7,7-Dimethoxynorbornene (30)
The synthetic equivalency of 7,7-dimethoxynorbornene (30) to oxonium
ion 29 is based upon the results of acidic hydrolysis of ketals in which
13
an oxo-carbonium ion is an assumed intermediate. Treatment of ketal 30
7


8
with a Lewis acid should provide the stabilized oxonium ion (29),
MeCL .OMe
v"e
Lewis
Acid
30
29
The ketal (30) is readily available from hexachlorocyclopentadiene (31)
via the three step reaction sequence illustrated in Scheme 2.1, as previ
ously described.^^
Yc:
,CI CH.OH p==:\vX>MeCIV^kH2
MeOvY)Me MeO\/OMe
CL
Cl K0H ^AOMe a
CL
¡Ul¡
CI^CI
EtOH
31
32
30
Scheme 2.1
Preparation of 5-Trimethylsilylcyclopentadiene (28)
The synthetic equivalence of 5-trimethylsilylcyclopentadiene (28)
for the cyclopentadienyl anion (_8) is perhaps less evident. There is by
now ample precedent for the reaction of allyl silanes with appropriate
electrophiles^ ^ in the presence of Lewis acids.
Nu-S¡R3 +


9
This reactivity has recently been extended to include additions to
ketals.^
OR
RO^
Sv
^=N/Sl"e3
RO.
* oz
Lewis Acid
RO
OR
i
At the initiation of our studies, however, there was relatively little
information on this aspect of our synthesis. Even to date there have
been no reported analogous studies of the electrophilic alkylation of
28 with ketals.
Treatment of a tetrahydrofuran (THF) solution of cyclopentadiene
with sodium metal, or preferably sodium hydride, provides the rose-
colored sodium cyclopentadienyl anion (8_), which then reacts with
20
trimethylsilylchloride (TMS-C1) to generate silane 28.
8 28
A complicating property of 28_ is its facile rearrangement to isomers
34 and 35., presumably via 1,5-hydrogen shifts, but if the reaction
is kept cold (<20 C), essentially most of the material isolated is


10
21 22 21
isomer _28. Ashe has reported an equilibrium ratio of 90:7:3 for
isomers _2<3, 34 and _35_, respectively, in which provides baseline
resolution of the NMR signals of the SiMe^ groups. In CDCl^,
isomers 34_ and _35 have identical SiMe^ chemical shifts, but isomer 28. is
23
resolved and is present to the extent of 87%. It may be noted that
this tendency of the trimethylsilyl group to favor substitution on the
5-position is remarkable compared to alkyl groups which seek out only the
1- and 2-positions. It has been reported that fractional crystalliza
tion by a successive partial freeze-thaw-filter technique affords pure _28
21
(mp -19C). This method was found to be too tedious in our hands for
synthetic scale; therefore, the isomer mixture (28, 34 and 35) was used
directly with no apparent ill effects.
Reaction of 7,7-Dimethoxynorbornene
with Trimethylsilylcyclopentadiene
After translation, a relatively simple one-pot synthesis of
methoxybisesquinene (26) now appears
Scheme 2.2
The problem becomes to find the proper reaction conditions to favor the
coupling. This primarily depends upon the choice of Lewis acid, solvent,
and temperature.


11
The reaction was run under a variety of conditions utilizing various
Lewis acids and solvents (see Table 2.1). Surprisingly, upon capillary
GC-MS analysis, we observed not only _26 in the reaction mixture but at
least three other (C^g^gO) isomers (see Figures 2.1 and 2.2). The yield
and ratio of these various isomers were very dependent upon the reaction
conditions, particularly the nature of the Lewis acid and solvent.
Scheme 2.3 summarizes these results and shows the major isomers obtained
(26 or 39). In addition, most reaction methods were accompanied by the
formation of a yellow polymeric material, which was insoluble in pentane,
and contained a relatively large amount of trimethylsilyl residues.
Separation of the crude reaction mixture by flash chromatography on
silica gel afforded a mixture of four isomers (ca. 8-57% yield).
It was extremely difficult to resolve this isomer mixture, but by careful
flash chromatography followed by preparative TLC or GC, the major isomer
(26 or 39) could be obtained relatively pure (>95%).
Structure Determination
Nuclear Magnetic Resonance
Fulvalene 36 was isolated as a minor product in the best yield
(2.5%) from Method A. The symmetrical nature of fulvalene _36_ was readily


Table 2.1. Representative Results of Reaction between Ketal J30 and Silane _28 under Various Conditions
Method
A
A
B
C
D
D
Isolated
Ketal 30
Silane 28
Lewis Acid
Solvent
Temp
Time
(hr)
Isomer Ratio
26 40? 38 39
Yield
(Isomer
Mixture)
500 mg
(3.25 mmole)
448 mg
(3.25 mmole)
A1C13
ch2ci2
-78C
1.3
(not available)
17%
(39)
1.0 g
(6.5 mmole)
0.9 g
(6.5 mmole)
A1C13
cii2ci2
-78C
1-2
14 2 10 63
8.7%
1.0 mL
(6.5 mmole)
0.9 g
(6.5 mmole)
A1C13
Et20
0C
3-4
(not available)
15-20%
(26)
1.0 mL
(6.5 mmole)
2 mL
(11.7 mmole)
BF3-Et20
ch2ci2
25C
1.75
77 8.8 14
29%
4.06 g
(26.3 mmole)
7.37 g
(53.4 mmole)
BF3-Et20
ch2ci2
5C RT
3.3
78.9 8.2 12.9
57%
5.0 g
(32 mmole)
8.97 g
(65.0 mmole)
BF3*Et90
cii3ci2
0-5C
1.5
79.2 0.6 7.3 13.0
55.8%


13
Figure 2.1. GC of reaction mixture (Method D) showing identification of
isomers.


14
B-se Peak = 128.0 Base Peak Abundance = 1664
* 1 l I 1 | 1-~1 1 I |-
50 10 150 200 250
Base Peak = 188.1 Base Peak Abundance = 3464
, Li l.
li
1
1
.111 Jlli
26
Ease Peak = 188.1 Base
150 20
Peak Abundance =
1--,-
25
1 122
ll i, ,
Ll I, jLuI...i
k jj
1 0 O
U|J|]
I '
150
39
' M 0
1
: =; m
MeO
108
173 (108)
Figure 2.2. Comparison of mass spectral fragmentation patterns for
compounds _36, _37_, 26_, _38^ 39.


15
13
apparent by inspection of its C NMR spectrum. At a short pulse delay,
the two quaternary vinyl carbon signals were missing, and only 5 signals
were observed: three vinyl carbons (=CH), one methyne (CH), and one
methylene (CT^). When the pulse delay was increased to allow for the
longer relaxation times (T^) of the quaternary carbons, 2 new peaks
appeared in the vinyl region. The NMR spectrum for _36 was also
characteristically symmetrical with a complex vinyl multiplet (6 6.4, 6H)
bridgehead multiplet (6 3.5, 2H), and endo/exo ethylene multiplets
(6 2-1.2, 2H, 2H).
Isomer 37_ equilibrated to form a ca. 50:50 mixture of 37a and 37b
13
as evidenced by doubling of peaks in the C NMR spectrum, with four Cf^
i
peaks, two CH peaks, two -OMe peaks, one small quaternary -C-OMe peak,
and nine vinyl peaks. In the NMR spectrum, the vinyl region contained
a multiplet for the cyclopentadienyl residues (ca. 6.2, 6H) and a close
triplet (6 6.0, 4H) which is characteristic of symmetrical 7-substituted
norbornenes. Farther upfield appeared two -OMe signals superimposed on
two sets of bridgehead and cyclopentadienyl methylene multiplets (ca.
6 3, 12H), followed by two well-separated multiplets for the endo and exo
ethylene hydrogens (6 1.6, 4H and 0.9, 4H, respectively).
From mechanistic considerations, we could predict at least four
other isomers. To distinguish among these possibilities, we made
use of existing molecular symmetry and in some cases created symmetry for
spectral simplification. Scheme 2.4 outlines the symmetry results after
reduction of the double bond in compounds 26_, _38_, _39 and 40 with the
bracket numbers indicating the total number of carbon signals expected in
13
C NMR.


16
Scheme 2.4
The structure for 26_ was confirmed by its expected simple eight-
13 1
line C NMR spectrum (due to its symmetry), with one quaternary (-C-),
one vinyl (=CH), four methyne (-CH), one methylene QCl^), and one -OMe
signals. The ^H NMR spectrum of _26 was also characteristic, with a
virtual triplet (J=1.9 Hz) for the two vinyl protons. At high field, a
pentet (J=2.95 Hz) was observed for H(3a) which arises from vicinal
coupling to bridgehead hydrogens H(3)-H(7a) and long-range "W" coupling
to endo hydrogens H(7) and H(8).
13
The C NMR spectrum for isomer 39_ was much more complex, with
13 resonances. The question of structure assignment between isomer 39.
and 38^ was resolved by taking advantage of the resulting symmetry of 38
after catalytic reduction of the double bond. Upon removal of the vinyl
carbons in .39, there still remained 13 resonances with two new carbon
signals. Analysis of the selective decoupled high field 300 MHz ^H NMR


17
spectrum was consistent with the structural assignment for _39 (see
Appendix 2).
The mixture of isomers 26. + _38 could not be resolved easily, but on
chromatography with AgNO^ impregnated silica gel, it was possible to
13
achieve a 40:60 enhancement (26_:33, respectively). A C NMR spectrum
for this mixture revealed 21 resonances, 8 of which were identified as
belonging to _26_, with 13 signals remaining. At this point, the identity
of 38 was still in question. Due to its asymmetry, isomer 40 was also
consistent with this spectrum. To distinguish between these two possibil-
13
ities, the mixture of 26. + _38 was catalytically reduced. The C NMR
spectrum of the resulting mixture exhibited only 16 signals, 8 of which
were again assignable to 26-H^. Therefore, the structure of 38 was
confirmed by its unusual symmetry after reduction.
The remaining postulated isomer 40 was not observed and from
mechanistic considerations is the least likely to be formed. A peak of
similar retention time as the other isomers was observed only in very low
amounts in the GC (<0.6%) and could not be isolated.
Mass Spectra
Examination of the 70 eV GC-MS obtained of the mixture of isomers is
particularly interesting (Figure 2.2). There is a striking similarity of
the spectrum for _37_ compared v/ith _36_. Apparently, isomer 37. fragments
initially (M+ MeOH = 156) and enters the fulvalene (M+ 156)
manifold. Both compounds exhibit a large 128 peak corresponding to loss
of ethylene to produce a stable fulvalene ion. For the remaining
isomers (26, 38 and 39), the parent ion (m/z 188) is observed as the base
peak in all cases. A very characteristic fragment ion (m/z 123) arises


18
due to a retro-Diels-Alder process (loss of C^H^-) and corresponds to the
intermediate oxonium ion produced in the reaction mechanism for 26. and 3£
(see Scheme 2.5).
Mechanism
The reaction mechanism apparently involves intermediate carbocation
species which can rearrange via various pathways leading to isomers 26,
37-40 as illustrated in Scheme 2.5. Presumably, when the Lewis acid
complexes with ketal _30, it promotes the loss of a methoxide moiety to
generate oxonium ion 29.. The silyl alkylating agent (28) may then
I
OMe OMe
26 39 38 40
Scheme 2.5


19
approach ion 29_ from either face (a_: syn to the double bond or _b: anti to
the double bond). Approach from the "wrong side" (_b) produces isomer 37_
after loss of the silyl group and rearrangement. Approach over the
double bond (ji) should be favored sterically to generate intermediate
ion 41, which can suffer either of two fates described by Path I or
Path II. Path I depicts direct loss of the silyl group followed by rapid
[4+2] closure to form _26. Alternatively, Path II depicts double bond
bridging of the intermediate cation _41_ to form U2_, which could undergo
Wagner-Meerwien rearrangement. Loss of the silyl group then promotes
closure by any of the four modes indicated to produce 26. and 39-40.
In the presence of BF^*Et20, _26 is formed preferentially, while
AlCl^ favors production of 39. These results may be rationalized by
considering that BF^^Et^O favors early loss of the silyl group (by F
displacement), with subsequent Diels-Alder cyclization producing _26^ as
the major isomer via Path I. On the other hand, AlCl^ is less nucleo
philic (toward silyl group displacement) and could favor a longer-lived
carbocation species, which subsequently undergoes further rearrangement
via Path II to produce predominantly isomer 39.
Improved Isolation of 26 from Isomer Mixture
An improved method of purification of 26. was devised which employed
a bromination/debromination procedure. A mixture of the isomers was
treated with B^/CT^Cl,-, to brominate the double bond. This gave rise to
a mixture of dibromides which were easily separated by flash chromatog
raphy on silica gel. The two major isomers isolated are depicted in
Scheme 2.6 (see Chapter 3 for further discussion of bromination). The
trans-dibromide (26-Brn) was crystalline and facilitated easy clean-up to


20
a high purity (>99% by GC). The debromination was attempted by treatment
25 26
under standard conditions of Zn/EtOH + acetic acid or Zn-Cu couple^
with heating. This gave little success with a large amount of rearranged
dibromide (43) being formed (apparently due to thermal rearrangement).
However, it was noted that utilizing these same conditions, with the reac
tion flask immersed in a sonicating cleaning bath, led to a quantitative
debromination in <5 min! It was then determined that bromination of a
clean sample (>97%) of 26. at -60 to -50 C led to pure 26-Br^, without
rearrangement.
This procedure now allows the rapid preparation of 26. in high yield
and purity as illustrated in the overall Scheme 2.6.


Scheme 2.6


CHAPTER THREE
REACTIVITY AND REARRANGEMENTS OF BISESQUINENE
Previous work in our group has investigated the solvolytic behavior
of bisesquinane brosylates to delineate the factors affecting rearrange-
27
ments of these systems. Apparently, there exists a delicate balance
between thermodynamic and bond alignment factors which affect the outcome
of rearrangements in these and other related systems. In the twist-
brendyl system (44), rearrangement into two manifolds is possible due to
28
direct participation by either of two adjacent C-C bonds.
Products derived from 45 predominate by 2.2:1 over those from 46., presum
ably due to more favorable C(1)C(6) bond alignment, even though 46 leads
to a more thermodynamically stable skeleton.
Interconversion of the Wagner-Meerwein related pair, 47 and 48, is
27
believed to involve the O-bridged cation 50. Acetolysis of brosylate
49 produces predominantly acetate 48-OAc with a small amount of acetate
47-OAc, possibly due to leakage from ion _51. to 50.
Acid catalyzed equilibration of acetates 47-OAc and 48-OAc produces the
product ratio 99.5% 48-OAc to 0.5% 47-OAc. This corresponds to a free
energy difference of 3.7 kcal mole Thus, the conclusion was made that
22


23
50 51
thermodynamic considerations favor the participation of bond C(3a)-C(3b)
27
in 48 despite the ideal C(2)C(8) bond alignment. These findings are
28
contrary to the results of the twistbrendyl system and underscore the
fact that both factors (bond alignment and thermodynamic product stabil
ity) must be carefully considered for prediction of Wagner-Meerwein
rearrangements.
Acid Catalyzed Rearrangements in Methoxybisesquinene
Previous results by Grob and co-workers have demonstrated the facile
cleavage on solvolysis of 6-exo-substituted-2-exo-norbornyl toluene-
sulfonates (52) by a concerted fragmentation involving rupture of the
C(l), C(6) bond in cases where the substituent is an -electron donor,
such as CH3S, CH30, HO, or (CH^N.29,30
52
53
54


24
31
These accelerated cleavages have been called "frangomeric effects" and
operate in the 6-norbornyl case to produce exclusively the intermediate
salts 53_ which are immediately hydrolyzed to (3-cyclopentenyl)acetalde-
hyde (54). Another example of this type of cleavage was reported by
32
Gassman and Macmillan for the ketal _55 which, on solvolysis followed by
reduction with lithium aluminum hydride (LAH), produced (3-cyclohexyl)-
methanol (57) in 57% yield.
Previous work on dimethyl ketal _58 showed no similar
instead produced the 2-exo-methoxy-7-norbornone (61)
33
group participation of the syn-methoxy moiety.
fragmentation but
via neighboring
OMe
58
59
SO
This difference of reactivity can be explained as a result of "tying
back" the syn-oxygen in ketal 55. to inhibit its participation and
thereby afford the anti-oxygen the opportunity to participate in the
frangomeric cleavage.
In view of the frangomeric effect, the results for the unsubstituted
bisesquinane (47) solvolysis and acid catalyzed rearrangements prompted
us to consider the effect of a methoxy substituent on carbon-3b (e.g.,
methoxybisesquinene, 26). Under acidic conditions (see Scheme 3.1), it


25
Scheme 3.1
was anticipated that the methoxy moiety should facilitate the leakage of
ion _62 to ion 63a and thence to the localized cation 63b. The presence
of ion 63b would be manifested by the formation of ketone 66. Solvent
capture by either ion 62. or ion 63a could produce products 64-X and 65-X
Product 64-X could also arise from direct addition to the double bond in
26 before rearrangement to ion 62.
Addition Reactions of the Double Bond
A series of electrophilic addition reactions to the double bond of
bisesquinene (26) were studied to gain insight into its unusual reactiv
ity and tendency toward rearrangement.
One of the first indications of this unusual reactivity was the
observation that the neat methoxybisesquinene (26) on standing several
months in the refrigerator partially decomposed to produce a polymeric
material and the exo-epoxide (67). This epoxidation is presumably due
to facile air oxidation of the alkene.


26
That this material was the exo-epoxide was demonstrated fay the authentic
synthesis of 67_ by treatment of _26_ with 3-chloroperoxybenzoic acid
(MCPBA), which produced the single exo-isomer _67_ (87% yield). The NMR
spectrum contained a very characteristic singlet (6 3.24, 211) for the
endo hydrogens adjacent to the epoxide confirming its expected exo stereo
chemistry.
Bromination of the double bond in methoxybisesquinene (26) at room
temperature produced a mixture of isomers 26-Br^ and 43_ (82% and 18%,
respectively).
The rearrangement to dibromide 43 probably proceeds via bromonium ion 68a
and a subsequent Wagner-Meerwein shift to 68b. When the alkene _26 is bro-
minated at -78 to -60C, only the crystalline trans-dibromide 26-Br^ is
produced with no evidence for the rearrangement product 43. The structure
of 26Br0 was confirmed by x-ray crystallography and is discussed in Chap
ter Four. Tna NMR spectrum for 26-Brp was distinctly different from


27
that of the rearranged dibromide 43, with elements of its pseudo-symmetry
apparent. The signal for H(3a) was still quite clearly a pentet
(J=2.7 Hz) in 26-Br^, while in 43 it was observed as a broad multiplet.
The most characteristic signals came from the protons alpha to Br at
6 4.53 (dd, J=2.7, 5.2 Hz) and 6 4.19 (d, 2.7 Hz), corresponding to the
exo and endo hydrogens, respectively, in 26-Br,-,. The corresponding
protons in 43 appeared at <5 4.85 (broad t, J=1.2 Hz) and 6 4.08
(t, J=1.46 Hz).
That the double bond of methoxybisesquinene (26) is particularly
susceptible to acid was first realized during the attempted de-methyla-
tion with trimethylsilyl iodide (TMS-I). This reaction is thought to
proceed by complexation of the ether oxygen with the silyl moiety fol-
lowed by S,,2 displacement of the methyl group by iodide.
R-O-Me + TMS-I R-0Me I > R-O-TMS R-OH
1
TMS Mel
Subsequent hydrolysis of the silyl ether produces the desired alcohol.
However, treatment of alkene 26_ with TMS-I did not produce the expected
alcohol. Instead, a complex mixture resulted which, upon GC-MS analysis,
indicated that addition of HI to the double bond had occurred. The major
product v/as isolated by prep GC and tentatively identified as exo-iodide
64-1 based on ^H NMR and MS fragmentation patterns.


28
The formation of HI could result from adventitious water present in the
reaction or upon quenching of excess TMS-I on work-up. Removal of the
double bond by reduction followed by treatment with TMS-I led to clean
production of the saturated alcohol (see Chapter Four), thus demonstrat
ing the sensitivity of the alkene to acid addition.
Preparation of Acid Rearrangement Products
To study the acid catalyzed rearrangements of _26_, we needed
authentic samples of the possible alcohols, acetates and ketone. The
epoxide 67_ was opened smoothly with diisobutylaluminum hydride (DIBAL-H)
to produce a clean sample of exo-alcohol 64-OH (78.5% yield). The Hi NMR
spectrum of exo-alcohol 64-OH exhibited a quite characteristic pattern of
doublet of doublets (6 3.94, J=2.4, 7.1 Hz) for the endo-hydrogen alpha
to the hydroxyl moiety. The carbon spectrum contained only 12 visible
peaks, but one was slightly more intense, suggesting overlap. The INEPT
pulse sequence confirmed the presence of 3 methylene peaks, two of which
were almost superimposed, indicating the molecule's more symmetrical
appearance at sites removed from the added functionality.
OMe
It was anticipated that the rearranged alcohol 65-OH could be
obtained by the reaction sequence as outlined in Scheme 3.2. This
approach depends upon a previously described rearrangement of epoxide 69


29
to alcohol 70, apparently via carbene insertion into the bridge C-H
69
70
Treatment of alcohol 71 with sodium hydride and methyl iodide cleanly
produced the methyl ether 72. (98% yield). Epoxidation was smoothly
accomplished with 3-chloroperoxybenzoic acid (MCPBA) to yield epoxide 73
(95% yield). Attempted rearrangement of epoxide 73 with lithium diethyl
amide in refluxing diethyl ether (Et20) gave only starting material on
work-up. However, refluxing in THF with lithium diethylamide produced
the desired alcohol 65-OH (53% yield). A point of confusion arose
initially in that both epoxide 73. and alcohol 65-0H had identical
retention times on the GC capillary column being utilized; however, the
transformation of 73 to 65-0H was readily distinguished spectroscopically
due to its loss of symmetry. The ^H NMR spectrum for 55-OH contained a
diagnostic doublet 4.3 (J=2.4 Hz) for the hydrogen alpha to the -OH,
13
which is quite characteristic for this twisted ring system. The C NMR
spectrum clearly indicated rearrangement of the symmetrical epoxide _62_
(8 signals) to the unsymmetrical alcohol 55-QH (12 signals, one peak
overlapped).
Ketone _66 was also obtained as previously described from alcohol _71_
37
by treatment with pyridinium dichromate (Scheme 3.2).


30
Scheme 3.2
Alcohols 64-OH and 65-OH were cleanly converted to their correspond
ing acetates by treatment with acetic anhydride in the presence of a
OO I I O
catalytic amount of dimethylaminopyridine (DMAP). The n and JC NMR
spectra were not significantly changed except for the observation of the
acetate residue.
Ac20
DMAi^
Results of Acid Addition to the
Double Bond of Methoxybisesquinene (26)
With the probable products of acid addition to methoxybisesquinene
in hand, it was now a simple matter to identify the rearrangement prod
ucts. The results of the treatment of methoxybisesquinene (_26^ with
various acids are summarized in Table 3.1. In no case was the formation
of ketone 66 observed.


31
Table 3.1. Acid Catalyzed Rearrangement of Methoxybisesquinene (26)
26
Add

R
Conditions
0
Product Ratio
0
II
cf3c- tfa/cdci3 90 10
RT, 12 h
0
II
CH3C- HOAc/TsoH 60 40
60C
30 days
H- H2S04/H20/THF 86 14
38% :21%:41%b
(1 : 1 : 2) vol
RT, 6 h
H- HS0,/Ho0/THF 36 64
2 4 2
60% :20%:20%
RT, 4 h
H- 40% HS0./H0
2 4 2
a) 60C, 2 h 24 76
b) 60C, 12 h <1 99
a Determined by capillary GC; no other significant products were
detected
b wt/wt%


32
Trifluoroacetic acid (TFA) adds rapidly at room temperature to
methoxybisesquinene (26) in CDCl^ solution, producing a 90:10 ratio of
64-TFA and 65-TFA, respectively. The 64-TFA isomer was isolated and
1 13
fully characterized. Its H and C NMR spectra were quite similar to
64-0Ac. The mixture of TFA-isomers was treated with DIBAL-H and con
verted cleanly to a mixture of alcohols 64-0H and 65-0H, for confirmation
of their structures by GC retention times.
Treatment of methoxybisesquinene (26) with glacial acetic acid and
catalytic tosylic acid, although much more sluggish, gave similar
results. The mixture was maintained at 60C for 30 days and resulted in
the partial equilibration of acetates 64-0Ac and 65-OAc (60:40, respec
tively), with ca. 18% unreacted methoxybisesquinene (26) remaining. To
assess the equilibration, acetate 64-0Ac was heated in glacial acetic
acid, 1% acetic anhydride, and catalytic tosylic acid at 75C. After
1 week, GC analysis indicated a relative ratio of 45:55, 64-0Ac to
65-0Ac, respectively. Allowing the equilibration to continue for an
additional week produced a relative ratio of 16:84. The equilibration is
clerly quite slow under these conditions. Noteworthy is the fact that
no additional products appeared.
The results of sulfuric acid catalysis indicate a significant
increase in the rearrangement of 64-OH to 65-0H with increasing acid
strength and temperature. Tetrahydrofuran (THF) was used as a cosolvent
to maintain solubility, however, analysis was complicated by the


33
formation of THF decomposition products. This problem was circumvented
by use of I^SO^/^O solutions without THF, and although this resulted in
a heterogeneous mixture, clean conversion of methoxybisesqinene 26. to
alcohols 64-OH and 65-OH was observed.
To determine the stability of ketone 66^ under these conditions, the
ketone was treated with acid as above (40% ^SO^/^O, 60C) for 2.5 hr.
Upon GC analysis, there was no trace of ketone _56, but a new peak was
observed at longer retention time (which had not been observed in any of
the previous acid rearrangements of methoxybisesquinene). The NMR
spectrum of the crude reaction mixture exhibited somewhat broadened peaks
suggesting a mixture of polymeric material. After prep TLC, a relatively
pure material was obtained, and its ^H NMR spectrum was remarkably simi
lar to that of 65-OH, exhibiting a characteristic doublet (5 4.4 ppm,
J=2 Hz)and a parent ion of 192 m/z in the GC-MS. This material is tenta
tively identified as the diol (74 and could originate as shown:
66
74
Confirmation of this structure was attempted by treatment of 65-OH
with TMS-I in C^D^ to effect de-methylation and hopefully produce diol
74. As the reaction was monitored in the ^H NMR, broadening of the
proton alpha to the -OH occurred, and a new methoxy signal began to
appear soon after the addition of TMS-I. At longer times, both methoxy
peaks diminished as a peak for methyl iodide developed. After standing
overnight, the signals for -OMe virtually disappeared. Following work-up,
gas chromatographic analysis confirmed the absence of starting material


34
(65OH) and showed two new major peaks at 5.23 min (25.8%) and 7.88 min
(68.2%) and two minor components at 7.63 min (2.82%) and 8.05 min (3.25%).
The peak at 5.23 min corresponded to the retention time for ketone 66.
but the later peaks were at longer times than diol _74_ (6.68 min). The
NMR spectrum showed a broadened doublet (6 4.8, J=2 Hz) which was quite
similar to the rearranged ring system but no evidence of a vinyl peak at
5 6.0 for ketone 66. Analysis of the mixture by GC-MS confirmed the
presence of ketone 66^ (M+ 174, 19%); however, the later peaks were
extremely broad due to decomposition on the column and, except for m/z
175 (10%), showed only mass fragments corresponding to ketone 66.
Analysis of the mixture by direct vaporization on the solids probe
allowed detection of a small molecular ion at m/z 302 (0.33%), a now
substantially larger peak at m/z 175 (100%, M+-I), and peaks for HI+
(128, 55%) and I+ (127, 33%), which indicate the formula C^HjrOI.
Therefore, the major component is tentatively identified as iodo-alcohol
78 which may be formed as shown in Scheme 3.3.
The NMR results may be explained by formation of an initial silane
complex (75) followed by rearrangement to ion 76 or 63a. Collapse of the
ion pair (76 or 63a) would produce 64-1 and 65-1, which would account for
the broadened alpha proton and shifted -OMe signals. A second equivalent
of TMS-I then complexes with the -OMe and after work-up produces iodo-
alcohols 77_ and 7_8. Since there was no observation of the ketone 66
vinyl during the reaction, we suggest the capillary GC results (peak at
5.23 rain) are due to thermal rearrangement in the injector of _78. with
loss of HI. This is consistent with the GC-MS observations which
utilized a packed glass column (more reactive surface for decomposition
compared to fused silica).


35
Scheme 3.3


36
Conclusions
Apparently the addition of the methoxy moiety to the C(3b) position
of bisesquinene has little effect as far as the predicted frangomeric
cleavage of bond C(3b)-C(3a) to produce ketone 66^. These results imply
that ion 63a does not contribute significantly to the rearrangement of
the bisesquinane skeleton since leakage to 63b and thence to ketone would
be expected. A better representation of ion 63a may be the degenerate
rapidly equilibrating ions (79a and 79b).
OMe
79a
79b
It is difficult to rationalize why we did not observe any ketone 66_ or
subsequent ketone-derived products, since the energy of bond C(3b)-C(3a)
cleavage should be regained by formation of the carbonyl. In addition,
39
strain energy calculations for the related hydrocarbon ring systems
show that the skeleton of 6(3 is ca. 4 kcal/rnole more stable than that of
65. However, additional strain is contributed by the double bond and
carbonyl and may significantly raise the strain energy of 66 to a level
comparable or even higher than that of 65-OH. As a consequence, there
would be little driving force for frangomeric cleavage to occur. Some
support for this argument is the rearrangement of ketone 6(3 under acid
conditions to the 65-X framework.


CHAPTER FOUR
STRAIN AND STRUCTURAL EFFECTS
IN THE BISESQUINANE SYSTEM
Relief of skeletal strain is frequently cited as a contributing
40
factor in rearrangements of polycyclic skeletons to more stable ones.
When predicting and interpreting these skeletal rearrangements, it has
been helpful to use computer calculations of strain energies to compare
41 42
molecular stabilities of possible products. In this fashion, the
chemist can gain insight into the complexities of a reaction, and more
accurately determine the probable fate of a rearrangement which could
follow more than one course. A study of the structure and inherent ring
strain in the parent bisesquinane (4_) and its effects on reactivity and
rearrangements is presented here. The goal of this study is to discrimi
nate between various C-C bonds in order to partition the overall ring
strain and assign the "most strained" portions of the molecule.
Strain Energy
MM2 Calculations
Molecular mechanics calculations of strain energy utilizing
43
Allinger's MM2 program were carried out on the parent bisesquinane
(4_) and compared with various derivations obtained by 1-bond cleavages
(see Figure 4.1). The molecular mechanics method calculates a geometry
for the molecule which minimizes its total energy. The amount of strain
37


a
Figure 4.1. A) MM2 calculations of strain energy
a Engler force field-^9
b Allinger force field (MM1)39
B) Representative strain energies


39
present is reflected by the extent to which the molecule's structural
parameters (bond angles and lengths) deviate from their ideal values in
order to reduce the molecule's total energy. As can be seen from
Table 4.1, the total steric energy (E) results from the summation of
several contributing energies: bond compression (or stretching), bond
bending (angle distortion), stretch-bend, van der Waals (non-bonded inter
actions between atoms or groups), and torsional (function of dihedral
angle). Inspection of these energy factors for compounds _4, 80-82 is
instructive in determining the major sources of high steric energy. In
all cases, the torsional interactions contribute greatly to the observed
steric energy. These bridged polycyclic systems, by their nature, force
sterically demanding eclipsing interactions which give rise to the ob
served large torsional energies (20-26 kcal/mole). Another major contri
bution to steric energy comes from the bending, which decreases substanti
ally (32-6 kcal/mole), as angle strain is relieved. Most of the other
energy factors are relatively insignificant, except for the van der Waals
1,4 interactions (4-9 kcal/mole). Interestingly, in the bisesquinane
skeleton (4_), these interactions are the lowest of the four compounds
compared.
The bond enthalpy (BE) and strainless bond enthalpy (SBE) can be
calculated from standard values for the total number and types of bonds
in the molecule. The partition function contribution (PFC) is the sum of
population (POP), torsional (TOR), and translation/rotation (T/R) contri
butions and is constant for all four structures due to their rigidity.
Utilizing these values and the steric energy (E), the heat of formation
(HFO) may be obtained from the following equation:
HFO
E + BE + PFC


40
Table 4.1. MM2 Energy Calculation Results (kcal/mole)
Compression
4
1.5970
80
2.144
81
1.409
82
0.970
Bending
32.332
22.211
15.598
6.074
Stretch-Bend
-1.375
-0.899
-0.546
-0.187
van der Waals <
fl ,4
4.345
7.481
8.917
6.479
Other
-2.043
0.597
-2.298
-2.356
Torsional
24.238
19.677
20.972
26.289
Total Steric Energy (E)
59.093
52.211
44.051
37.269
Bond Enthalpy (BE)
-50.72
-57.28
-57.28
-57.28
Strainless Bond Enthalpy (SBE)
-42.70
-49.29
-49.29
-49.29
Population (POP)
0.00
0.00
0.00
0.00
Torsional (TOR)
0.00
0.00
0.00
0.00
Translation/Rotation (T/R)
2.40
2.40
2.40
2.40
Partition Function
Contribution (PFC)
2.40
2.40
2.40
2.40
Heat of Formation
(HF0) = E + BE + PFC
10.77
-3.67
-10.83
-17.61
Strainless Heat of Formation
(HFS) = SBE + T/R
-40.30
-46.89
-46.89
-46.89
Inherent Strain
(SI) = E + (BE-SBE)
51.07
43.22
36.06
29.28
Strain Energy
(S) = POP + TOR + SI
51.07
43.22
36.06
29.28


41
The strainless heat of formation (HFS) results from the translation/rota
tion addition to the strainless bond enthalpy (SEE):
HFS = SBE + T/R
The inherent strain (SI) is calculated by adding the steric energy (E)
to the difference between the bond enthalpy (BE) and strainless bond
enthalpy (SBE):
SI = E + (BE SBE)
Finally, the strain energy (S) is obtained by correcting the inherent
strain (SI) for any torsional (TOR) and population (POP) contributions:
S = SI + TOR + POP
These results predict the greatest relief of strain (ca. 22 kcal/mole)
when cleaving the central bond _c which correlates well with previous
g
experimental observations. Thus, in the case where this bond is substi
tuted with diester groups (10), facile cleavage occurs to produce the
tetraquinacene 13.
E
10 13
Homoketonization
The calculated strain energies of SO and 81_ reveal a 7 kcal/mole
preference for breaking bond _b over bond a_ in bisesquinane (4_). To


42
devise an experimental test for the relative bond strengths of a and _b in
the bisesquinane system (i.e., which is more highly strained?), we consid-
44
ered a homoketonization type rearrangement. Generally, this can be
considered as the reverse homo-enolization process depicted below for
camphenilone (83)
83
Homo-enolization
Homoketonization
There are numerous examples of base-induced homoketonization, from
which some general factors relating to control of the regiochemistry of
the cleavage can be obtained. Relief of strain, product stability, and
the stability of the incipient carbanion are the major considerations for
determining regiochemistry. For example, preferential cleavage of bond a.
in 85 results from the delocalization of the incipient carbanion (86) and
46
produces aldehyde 88_ exclusively.
Relief of strain and product stability dictate bond cleavage in 89 which
47
leads to the formation of noradamantone (90).


43
39 90
The bisnoradaraantyl alcohol (91) horaoketonizes in t-BuOK/t-BuOD (70C) to
yield exclusively 92_, resulting from cleavage of bond a_ with retention
of configuration.^
In the case of the hydroxybisesquinane skeleton (93), these concepts
were utilized to probe the relative bond strain of a_ and _b as illustrated
in Scheme 4.1. If homoketonization occurs, a choice of which bond(s) to
break must be made. Cleavage of bond a_ would lead to "homo-enolate" _94
while cleavage of bond _b would produce "homo-enolate" 95.. Inspection of
molecular models indicates that in 94, the carbanion is rigidly held in
close proximity to the newly formed carbonyl (unlike the intermediate
95
Scheme 4.1


44
carbanion in the transformation of 9l_ to 92). Hence, we might expect
rapid equilibration to reform bond a_. However, this is not the case in
the formation of £5 since, due to the greater flexibility of the newly
opened cyclohexyl ring, the carbanion is removed from the vicinity of the
carbonyl. Thus after equilibration, we would expect to produce the more
thermodynamically stable ketone via "homo-enolate" 95.
Armed with these predictions, we attempted to confirm them experimen
tally (Scheme 4.2). In this regard, methoxybisesquinene (26) was con
verted by reduction to methoxybisesquinane (26-H^). This v/as cleanly
de-methylated to the crystalline bisesquinol (96) by treatment with
trimethylsilyliodide (TMS-I). The bisesquinol (96) was subjected to
homoketonization conditions similar to those utilized for 9J_ (t-butoxide/
t-butanol, 90C, 20.75 h), and GC analysis indicated only starting
material present. Under more vigorous conditions (200C, 22 h) GC analy
sis indicated a mixture of starting material (20%) and a single major new
component (72%). The mixture was fractionated by prep TLC to afford a
-1 13
ketone, as evidenced by IR (1740 cm ). The C NMS spectrum showed the
presence of 12 peaks, thereby excluding ketone _97 (by symmetry only
1 3
7 peaks are expected). The INEPT C NMR spectrum (Figure 4.2) clearly
shows the presence of 5 methylene peaks and 6 methine peaks, consistent
with the structure of ketone 98.
In summary, we have shown that exclusive cleavage of bond _b occurs
to produce the more stable ketone 98. in preference to ketone 97.


45
Homoketonlzation
Scheme 4.2


Figure 4.2.
INEPT 13C NMR
spectrum of ketone 98.


47
Bisesquinane Structure: Calculated and X-Ray
Bond Lengths
From the MM2 calculations, we can obtain structural information
regarding bond lengths and bond angles. One might suspect that a more
strained bond, as a consequence, would be longer than normal. Close
inspection of the calculated bond lengths of bisesquinane (4^
(Figure 4.3) reveals that bonds a_ and c_ are the longest bonds. That
this is indeed significant becomes more obvious when comparison is made
with compounds 80 and 81_. There is a clear trend indicating that as the
strain is relieved in the molecule, the bond lengths tend toward the
normal C-C bond distance of 1.54 X.
To substantiate the theoretical prediction of longer bond lengths
for bonds a_ and c_, an x-ray crystal structure was obtained for the
dibromomethoxybisesquinane derivative (26-Br^). An ORTEP drawing of
the crystal structure for 26-Br9 is presented in Figure 4.4 and a summary
of the bond lengths in Tables 4.2 and 4.3.
Figure 4.4. Stereoscopic view of the molecular structure of 26_-B^


48
Figure 4.3.
MM2 calculated bond lengths.


49
O _
Table 4.2. Bond Lengths [A] with Estimated Standard Deviations in
Parentheses for Dibromide 26-Br^ Involving Non-H Atoms
Br(1)-C(2)
1.968(8)
Br(2)-C(3)
1.987(8)
C (2 ) C (1)
1.500(11)
C(3)-C(4)
1.490(12)
C(1)C(12)
1.530(12)
C(4)-C(5)
1.549(11)
C(l)-C(ll)
1.556(10)
C(4)-C(ll)
1.561(11)
C(9)C(12)
1.539(12)
C(6)-C(5)
1.515(12)
C (9) C (8 )
1.523(13)
C(6)-C(7)
1.523(13)
C(9)C(10)
1.516(11)
C(6)-C(10)
1.553(11)
C (2) C (3 )
1.515(12)
C(7)-C(8)
1.538(13)
C(5)C(12)
1.612(11)
C(10)-C(ll)
1.588(11)
od)-c(io)
1.423(9)
0(1)C(13)
1.398(10)


50
Table 4.3. Bond Lengths [A] for Dibromide 26-Br? Involving H Atoms
H( 2)C(2)
1.16
H (1) C (1)
0.98
H(12)C(12)
1.04
H(9)-C(9)
1.11
H (81) C ( 8)
1.00
H (8 2) C (8)
1.15
H(ll)-C(ll)
1.00
H(M2)-C(13)
0.74
H ( 3) C (3)
1.06
H(4)-C(4)
0.94
H(5)C(5)
1.14
H(6)C(6)
1.16
H(71)-C(7)
1.01
H ( 7 2 ) C ( 7)
1.01
H(M1)C(13)
0.95
H(M3)-C(13)
0.95


51
The bond lengths are grouped according to similar bond types for facility
of comparison. It is immediately obvious that the conclusions based upon
M2 calculated bond lengths are reflected in the long bond lengths of
a [C(10)C(11) = 1.488 A] and c_ [C(5)C(12) = 1.612 A] in the crystal
structure of 26-Br^. It appears that the tendency of the bisesquinane
skeleton is to relieve large strain contributions by stretching these two
bonds.
Bond Angles
Marked distortion of bridgehead angles from tetrahedral has been
49
cited as a major source of skeletal strain. Calculation by MM2 of bond
angles in 4_, 80 and 8_1 (Figure 4.5) reveals cases of substantial compres
sion and accounts for a large portion of the strain energy of these mole
cules. Comparison of bond angles in norbornane^ with those calcu
lated for bisesquinane (_4) is very informative. As expected, the
central bridge angle C(1)C(11)C(4) at 93.0 is approximately equal to
the norbornane bridge angle of 93.1. Somewhat surprising is the angle
C(5)-C(4)-C(ll) which is compressed even more to 91.4! This compares
with the similar norbornane angle at 101. Careful examination of the
model of bisesquinane reveals that this unusual bond angle is a conse
quence of the molecular framework. Viewed from a different perspective
(Figure 4.6), this "bridgehead" carbon (in the sense of norbornane)
becomes a "bridge" carbon; consequently, the 91.4 bond angle appears to
be somewhat more normal.


52
Figure 4.5
MM2 calculated bond angles=and Z values
(see text).


53
Table 4.4. Bond Angles [] with Estimated Standard Deviations in Paren
theses for Dibromide 26-Br
Br (1) C ( 2) C ( 3)
110.6(6)
Br (1) C ( 2) C (1)
113.7(6)
C (1) C (2 ) C (3)
104.2(7)
C(2)C(1)C(11)
104.7(6)
C(2)C(1)C(12)
115.8(7)
C(11)C(1)C(12)
93.8(6)
C(1)C(12)C(9)
98.7(6)
C(1)C(12)C(5)
102.4(6)
C(5)C(12)C(9)
101.4(6)
C (12) C (9) C (8)
114.6(7)
C(12)C(9)C(10)
93.2(6)
C (10) C (9) C (8)
105.9(7)
C (9) C (8) C (7)
103.8(7)
C(l)-C(ll)-C(10)
103.0(6)
C(11)C(10)C(9)
104.9(6)
C(1)C(11)C(4)
92.6(6)
C(9)C(10)0(1)
113.1(6)
C(ll)-C(10)-0(1)
117.2(6)
Br(2)-C(3)-C(2)
110.3(6)
Br(2)-C(3)-C(4)
112.2(6)
C(4)-C(3)-C(2)
104.1(7)
C(3)-C(4)-C(ll)
107.5(6)
C(3)-C(4)-C(5)
112.0(7)
C(ll)-C(4)-C(5)
93.2(6)
C(4)-C(5)-C(6)
99.7(6)
C(4)-C(5)-C(12)
101.6(6)
C(12)-C(5)-C(6)
103.1(6)
C(5)-C(6)-C(7)
113.7(7)
C(5)-C(6)-C(10)
92.4(6)
C(10)-C(6)-C(7)
105.9(7)
C(6)-C(7)-C(8)
103.6(7)
C(4)-C(ll)-C(10)
103.1(6)
C(ll)-C(10)-C(6)
104.9(6)
C(9)-C(10)-C(6)
94.8(6)
C(6)-C(10)-0(l)
119.0(6)
C(10)-0(l)-C(13)
113.8(6)


54
Table 4.5. Bond Angles [] for Dibromide 26-Br Involving H Atoms
H(2)-C(2)-Br(l)
109
H(3)-C(3)-Br(2)
109
H (2) C (2) C ( 3)
107
H(3)-C(3)-C(2)
118
H ( 2) C (2 ) C (1)
112
H(3)-C(3)-C(4)
104
H (1) C (1) C (2)
115
H (4) C (4 ) C (3)
117
H(1)C(1)C(11)
112
H(4)C(4)C(11)
107
H(1)C(1)C(12)
114
H (4) C (4) C (5)
117
H(12)C(12)C(1)
121
H (5) C (5) C (4)
120
H(12)C(12)C(5)
114
H(5)C(5)C(12)
111
H(12)C(12)C(9)
116
H (5) C (5) C (6)
119
H(9)C(9)C(12)
110
H (6) C (6) C (5)
112
H(9)C(9)C(10)
110
H(6) C(6)C(10)
112
H (9) C (9) C (8)
119
H (6) C (6)C (7)
118
H(81)-C(8)-C(9)
122
H (71) C (7) C (6)
109
H (81) C (8) C (7)
102
K (71) C (7) C (8)
112
H(81)-C(8)-H(82)
98
H(71)C(7)H(72)
109
H (8 2) C (8) C C 9)
115
H (7 2 ) C (7) C (6 )
109
H (8 2) C (8) C (7)
116
H (7 2 ) C (7) C (8 )
114
H(11)C(11)C(1)
118
H (11)C(11)C(4)
121
H(11)C(11)C(10)
116
H(M1)C(13)0(1)
108
H(M2)C(13)0(1)
113
H(M3)-C(13)-0(1)
106
H(M1)-C(13)-H(M2)
79
H(M1)-C(13)-H(M3)
116
H(M2)-C(13)-C(M3)
131


55
Figure 4.6. Perspective drawings of bisesquinane (4J).
One method of gauging bridgehead angle distortion is to compare the
sum of the three internal skeletal angles around the central bridgehead
carbon (Z value, Figure 4.5). The Z value for norbornane is 311 which,
when compared to the normal tetrahedral arrangement (£ = 328.5 from
109.5 x 3) indicates significant angle distortion. Inspection of
Figure 4.5 reveals a trend in the Z values for compounds 4_, 80 and 81.
Apparently in bisesquinane (_4), C(11) and C(5) possess significantly
more angle strain than C(4). Cleavage of bond a or _b (GO or _81) results
in a substantial increase of the Z value for C(5), thus indicating a
decrease in angle distortion (i.e., the values become much more tetrahe
dral-like as bonding restrictions are relieved).
13
C-ii Spin-Spin Coupling and Angle Strain
13
It is well known that the C nuclear spin-spin coupling constant
appears to be a linear function of the amount of s-character in the
carbon-hydrogen orbital.A linear relationship has been demonstrated
between the nuclear spin-spin coupling constant and C-C-C bond
52
angles in simple cyclic hydrocarbons. This correlation has been
attributed to a change in hybridization to increase the s-character in
external bonds as internal bond angles are decreased. It has been
suggested that the decreased internal skeletal bond angles of norbornyl


56
derivatives require an increase in the p-character of the bridgehead car-
49
bon bonds. As a result, there is an increase in the s-character of the
53
bridgehead C-H bonds. Although estimates of % s-character have been
made using the simple relationship % s = Jj-,_^/500, quantitative extrapola
tion of % s-character in strained systems directly from ^ is not now
considered justified.'^ However, one can still make qualitative com
parisons of angle strain by inspection of coupling constants.
Figure 4.7 summarizes the coupling constants for methoxybisesquinene (26)
along with values for other related bicyclic systems. Based on our previ
ous analysis of angle distortion in bisesquinane (£ values), we predicted
enhanced s-character (and consequently larger coupling contants) for
C(ll) and C(5); however, there is no apparent correlation. Noteworthy is
the unusually high value coupling constant for the central carbon C(5)
(J=150.8 Hz) when compared to C(l) (J=144.6 Hz). The effect of decreas
ing skeletal bond angles can be seen clearly by comparing bicyclo[2.2.2]-
octene (J=134 Hz) with norbornene (J=145 Hz). Considering norbornane,
norbornene and norbornadiene, there is an obvious trend of increasing
in the bridgehead carbons as the ring strain is increased (ca. 3 Hz/
double bond). The bridgehead [C(4) and C(6)] coupling constants for
methoxybisesquinene correlate reasonably weil to what one might predict
based on a simple "fusion" of norbornadiene and norbornane.
Interplanar Angles
An unusual consequence of the molecular framework in bisesquinane
(4_) is the "tying back" of the two bridging methylenes by bond a. This
structural effect may be seen clearly in the crystal structure of 26-Bro
as viewed down the C(5)-C(12) bond (Figure 4.8).


57
0Me
135
136 134
132-2
131-134
55,56
Figure 4.7.
13C-H Coupling constants.


58
Figure 4.8. Crystal structure of 26-3r^ as viewed down the C(5)C(12) bond.
Interplanar angles were calculated by a least-squares type analysis for
26-Br^, from x-ray crystal data, bisesquinane (4.) and exo-exo-sesquinor-
49
bornane (80) from MM2 structures, and norbornane (Figure 4.9). The
results show a substantial opening of the exo face of bisesquinane
(136.7), compared to norbornane (123.5). Interestingly, the exo face
of sesquinorbornane (80) is compressed (117.4) due to van der Waals
replsions between the internal bridge hydrogens.
Diels-Alder Reactivity of Bisesquinene:
Adduct Stereochemistry
It is well established that norbornene is a reasonably reactive
dienophile in Diels-Alder reactions with activated dienes and generally
gives exo adducts.^ Because of its structural similarity with norbor
nene, we have investigated the reactivity of methoxybisesquinene (26^) as
a novel dienophile. It was anticipated that the greater accessibility of
the exo face of methoxybisesquinene may affect the stereochemistry of the
resulting adducts.


OMe
Figure 4.9. Interplanar angles.


60
The determination of Diels-Alder adduct stereochemistry has been the
subject of many investigations utilizing various chemical and physical
methods including Cope rearrangements,intramolecular cyclization,^
NMR proton-proton coupling,^ solvent induced shift method,^ phenyl
62 63
multiplicity method, and x-ray crystallography. All of these methods
suffer from limitations v/hich have hampered research in this area.
A fairly recent addition to the list of physical methods utilizes
13
coupled C NMR to probe adduct stereochemistry. It has been shown that
3
^C-H couPlin§ :*-s dependent upon the torsion angle

64-
nuclei in a Karplus-type relationship. The method is particularly
useful for bridged carbonyl adducts of tetraphenylcyclopentadiene (tetra-
cyclone) and has been called the "carbonyl multiplicity technique."0^
The adduct 99. derived from tetracyclone and diethyl fumarate exhibits a
doublet (J = 7.1 Hz) for the carbonyl resonance in the coupled C NMR.
The splitting results from long-range coupling only between the carbonyl
and the endo proton (H-2, j) = 160-170) since the exo proton (II3) is
improperly aligned ((¡) = 90). Consequently, it is now a simple to distin
guish between exo and endo adducts by examination of the long-range car
bonyl coupling patterns (eg., 100 = triplet, 101 = singlet).
99
100
101


61
Preparation of Adducts
Diels-Alder adducts of methoxybisesquinene (26) were prepared from
the dienes tetraclorodimethoxycyclopentadiene (102) and tetracyclone
(104). A benzene solution of methoxybisesquinene (26) and tetrachloro-
dimethoxycyclopentadiene (102) was heated at 80C for 10-12 hr to cleanly
produce the single crystalline adduct 103 (69% yield).
(endo, exo) (exo, exo)
Tetracyclone (tetracyclone, 104) is a much less reactive diene than
ketal 102 and requires more vigorous conditions for reaction with 26.
Tetracyclone has a characteristic deep purple color which disappears upon
cycloaddition and thus provides a convenient indicator of the reaction
progress. Gentle heating to melt a 1:1 mixture of methoxybisesquinene
(26) and tetracyclone (104) produces the crystalline adduct 105 and a
substantial amount of the decarbonylated diene 106 (25% and 68% yield,
respectively). The mixture was cleanly separated by prep TLC (benzene)
to remove the unreacted purple tetracyclone (104) and the decarbonylated
diene (106) which showed a characteristic blue fluorescence under UV
light. Adduct 103 melted with decomposition (mp 215 dec) to liberate CO
and also turned pink indicating some retro-cycloaddition back to tetracy
clone. This behavior is quite normal for tetracyclone adducts which have
62
been shown to readily decarbonylate.


62
Stereochemistry
The exo stereochemistry (with respect to the bisesquinane ring
system) of the adduct 103 was confirmed in the NMR spectrum by the
lack of vicinal coupling between the endo hydrogens H-1,2 (6 2.64, s) and
bridgehead hydrogens H-3,7a (6 2.32, d, J=2.7 Hz; coupled to H-3a). The
relative stereochemistry of the dimethoxy bridge is not readily discern
ible. However, by steric arguments we would predict the stereochemistry
as shown for adduct 103a (endo, exo) rather than adduct 103b (exo, exo)
due to the incursion of extensive van der Waals repulsions between the
methoxy and bridge hydrogens in the transition state for formation of
103b. To rigorously prove the stereochemistry of 103 required the trans
formation of the ketal to a carbonyl moiety. It has been reported that
trimethylsilyliodide (TT1S-I) is effective in the hydrolysis of ketals to
66
produce ketones. Treatment of adduct 103 with TMS-I resulted in selec
tive demetnylation, producing alcohol 107 v/ith the ketal moiety remaining
intact, presumably due to steric hindrance by the flanking chlorine atoms


63
as well as inductive retardation of initial oxygen coordination to sili-
1 13
con prior to the first deraethylation step. The H and C NMR spectra
of 107 were not significantly changed from that of 103a except for the
absence of the methoxy signal.
When adduct 103 was subjected to cold H^SO^ (cone), clean conversion to
the ketone 108 resulted.^ The fully coupled NMR spectrum of ketone
108 shows no long-range coupling of the carbonyl (6 186.87), thereby
confirming its assigned stereochemistry and that of adduct 103a as endo,
exo.
The stereochemistry of adduct 105 was similarly established to be
the exo adduct of methoxybisesquinene due to the lack of vicinal
coupling (6 2.97, H-1,2, s). Previously, the tetracyclone adduct of
norbornene had been assigned the endo, exo (110a) configuration based
62
principally on the phenyl multiplicity patterns.


64
By analogy, we fully expected the methoxybisesquinene-tetracyclone adduct
to be endo, exo (105b) as well. That this was not the case was clearly
13
demonstrated by the C NMR carbonyl multiplicity ( 202.7, J=7.0 Hz, t)
which dictates the exo, exo stereochemistry for adduct 105a. Somewhat
62
puzzled by this discrepancy, we prepared the norbornene-tetracyclone
adduct (110) for direct comparison with 105a (see Figure 4.10). The
13
coupled C NMR spectrum of 110 exhibited a triplet for the carbonyl
(6 202.1, J=6.9 Hz), thereby necessitating the reversal of the stereo
chemical assignment for the norbornene adduct to 110b (exo, exo).
These results may be explained by considering the facile cyclorever
sion which often occurs in some Diels-Alder adducts and has been shown to
equilibrate the kinetically formed endo adducts to the more stable exo
adducts (e.g., maleic anhydride endo adducts equilibrate to exo on heat
ing). Additionally, it has been noted that decarbonylation occurs more
readily for endo tetracyclone adducts, presumably due to relief of strain
68
and favored stereo electronic alignment. Since the reaction conditions
promoted extensive decarbonylation, it is conceivable that our results
reflect only the thermodynamic product being isolated. Preliminary
results for the adduction of tetracyclone to norbornadiene at room temper
ature indicate that the endo, endo isomer is formed exclusively. If a
chloroform solution of this adduct is warmed, rapid cycloreversion occurs
as evidenced by the purple color. Thus, we must conclude that a delicate
balance exists for the preference of stereochemistry in tetracyclone
adducts, the nature of which is still little understood.


65
Figure 4.10. Carbonyl multiplicity patterns.


66
Suggestions for Future Work
An interesting synthetic application for these bridged ketone
adducts of methoxybisesquinene was suggested by inspection of the mass
spectral fragmentations of adducts 108 and 105a. After loss of CO, the
tetrachloroketone 108 fragments quite readily into tetrachlorobenzene and
a triquinocene derivative (111) (C^H^O, m/z 162, 49% rel intensity).
The tetracyclone adduct 105a behaves similarly with initial loss of CO
(m/z 544, 100% rel intensity) followed by loss of C-^H-^O to produce
^30^22 382, 25% rel intensity) which corresponds to tetraphenylben-
zene. Thus, as outlined in Scheme 4.3, a thermal cycloreversion process
should extrude the tetrasubstituted benzene derivative 112 with concom
itant formation of the novel bridgehead substituted tetraquinacene 111.
R
OMe
R= Cl or 2
112
111
Scheme 4.3


CHAPTER FIVE
EXPERIMENTAL
General
Melting points were recorded using a Thomas-Hoover capillary melting
point apparatus and are uncorrected. Analyses were performed by Atlantic
Microlab, Inc., of Atlanta, Georgia.
Proton NMR spectra were run on either a Varan EM-360, a JEOL FX-
100, or a Nicolet 300 spectrometer. Chemical shifts were recorded
relative to tetramethylsilane (TMS) at 6 0.00. After the chemical shift,
values are given in parentheses for the multiplicity of the peaks, the
apparent splittings (J) where applicable, and the relative integration.
The symbols used for multiplicities are: s = singlet, d = doublet, t =
triplet, q = quartet, pent = pentet, and mult = multiplet.
Carbon NMR spectra were recorded on a JEOL FX-100 instrument with
chemical shifts relative to the deuterochloroform reasonance at 77.00.
After the chemical shift, values are given in parentheses for the multi-
69
plicity of the peaks as determined by off-resonance or INEPT decoupling.
i 1 s
The symbols used are: s = -C-, quaternary; d = -CH, methine; t = ^CH^,
methylene; and q = -CH^, methyl.
Infrared spectra were recorded on a Perkin-Elmer 283B spectrophotom
eter. The KBr pellets were made of the solids, and the liquids were run
neat betv/een NaCl windows.
Mass spectra were obtained either on an Associated Electronics
Industries (AEI) model MS-30 mass spectrometer at 70 eV equipped with a
67


68
Nova Systems 4 computer or on a Nicolet Fourier Transform mass spectrom
eter model FT/ms 1000.
Analytical gas chromatography was performed with a Hewlett-Packard
5880A equipped with a flame ionization detector and a cross-linked
dimethylsilicone capillary column (fused silica, 12.5 m x 0.2 mm ID).
The standard temperature program conditions were 80C (1 min), then
20C/min to a maximum temperature of 250C (15 min). All retention times
are reported under these conditions, unless otherwise specified.
Preparative GC was performed with a Varian Associates model A-90-P
utilizing a thermal conductivity detector, and a 10% SE-30 on Chromosorb
W (6 ft x 1/4 in).
70
Flash chromatography was performed as described by Still utilizing
MCB 230-400 mesh silica gel. All solvents were distilled prior to use or
were HPLC grade.
Analytical and preparative thin layer chromatography (TLC or prep
TLC were performed on glass-backed E. Merk TLC plates (silica gel
60 F-254), which were cut to the desired size with a diamond scribe glass
cutter. The spots were visualized either by UV fluorescence quenching or
adsorption of I2. A useful technique for prep TLC staining was to place
a thin strip of filter paper (soaked in an 12/pentane solution) on the
edge of the developed TLC plate. This was covered with a glass plate.
Adsorption of the iodine by the sample on the TLC plate allowed the
selective staining of only a small portion, thereby visualizing the
sample streaks.


69
Synthesis
Preparation of 7,7-Dimethoxynorbornene (30)
The reaction sequences were carried out as previously described to
14
afford 30. Specific details of a sample procedure are given below.
An aliquot of 5,5-dimethoxytetrachlorocyclopentadiene (32, 200 g)
was placed in a Pyrex gas scrubber tube which contained a frit in the
bottom and was fitted with a condenser. The ketal 32. was heated in an
oil bath (160-170C) while bubbling a gentle stream of ethylene gas
through solution. After ca. 48 h, NMR analysis of an aliquot indi
cated loss of the -OMe peak for 32. (6 3.30) and two new -OMe peaks for 33
(6 3.50, 3.55). The crude material was purified by bulb distillation
(kugelrohr apparatus available from Aldrich; 95-100C at 0.2 mm Hg) to
afford 32. as a colorless oil which crystallized at room temperature.
The chlorinated ketal _32_ was dechlorinated by the improved method of
Lap and Paddon-Row^ using sodium/EtOH as follows. A sample of tetra-
chloroketal _32 (5.37 g, 0.021 moles) was placed in a flask equipped with
a mechanical stirrer, ^ inlet, and a condenser. Absolute EtOH (100 mL)
was added followed by the addition of small pieces of clean sodium (ca.
15 g) until no more would dissolve in the refluxing solution (small beads
of liquid Na formed on the surface). The reaction was then cautiously
quenched by the addition of MeOH to consume unreacted Na, and the mixture
was poured over crushed ice. The aqueous mixture was extracted with Et20
(3x100 mL). The combined ether extracts were washed with brine until the
washings were clear, dried (MgSO,), and solvent removed in vacuo to
afford the dechlorinated ketal _30_ as a yellow oil (2.15 g, 67% yield, 90%
pure by GC). The ketal was subsequently purified by fractional


70
distillation with a 6 in vigereaux column and reflux head (7-10 mm Pig,
bp 48-54C, 97% pure by GC).
The Hi NMR spectrum (CDCl^, 60 MHz) contained the following
resonances: 6 6.05(t, J=2.0 Hz, 2H), 3.20(s,3H), 3.15(s,3H), 2.76(m,2H),
2.18-1.68(m,2H), 1.06-0.78(m,2H).
13
The proton decoupled C NMR spectrum (CDCl^ contained the following
6 resonances: 132.51(d), 117.94(s), 50.97(q), 48.44(q), 43.37(d),
22.22(t).
The mass spectrum (70 eV) had m/z (% rel intensity): 154(M+,20),
139(15), 123(35), 107(22), 95(15), 91(18), 79(100), 77(22), 59(34),
55(16), 45(22).
Preparation of 5-Trimethylsilylcyclopentadiene (28)
Trimethylsilylcyclopentadiene (28) was prepared as previously
20
described but with the substitution of NaH for Na sand. Freshly
distilled cyclopentadiene (33 g, 0.5 mole) was added dropwise via cannula
to a flask containing NaH (12 g, 0.5 mole) and dry THI (250 mL) which was
fitted with a reflux condenser, magnetic stir bar, and argon inlet. With
each addition, smooth evolution of P^ occurred. When all of the NaH was
consumed, the rose-colored THF solution of sodium cyclopentadienide was
cooled (-10C to 0C). To the stirred solution, TMS-C1 (54 g, 0.5 mole,
ca. 63 mL) was added dropwise over a 1 hr period. The ice bath was
removed and the reaction stirred for an additional 3 hr. The reaction
was quenched by the addition of Ho0 (5 mL) (note: a better procedure
would be to use MeOH instead), and the contents of the flask decanted to
leave behind a brown sludge (soluble in H2O) The excess THF was removed
in vacuo (no heat), washed with F^O, and finally extracted into Et20.


71
The Et^O extracts were dried (Na2S0^) and solvent removed in vacuo.
Capillary GC (50C to 200C at 10C/min) indicated two major components:
silane 28. (2.59 min, 47.6%) and an unknown high boiling material
(6.50 min, 33.5%, possibly trimethylsilanol). Pure silane _28^ was
obtained by fractional distillation (11 mm Hg, bp 29C, 97% pure by GC).
Reaction of 7,7-Dimethoxynorbornene (30) with 5-Trimethylsilylcyclopenta-
diene (28)
Method A: A1C13/CH2C12, -78C.
To a 50 mL flask fitted with an addition funnel, magnetic stir bar,
O
and N2 inlet, were added dry CH2C12 (10 mL, 3 A molecular sieves) and
AlClg (520 mg, 3.9 mmole). The mixture was cooled to -78C (dry ice/ace
tone), and a mixture of 7,7-dimethoxynorbornene (30, 500 mg, 3.25 mmole)
and TMS-cyclopentadiene (28, 448 mg, 3.25 mmole) was dissoved in 10 mL
dry CH2C12. This was added dropwise to the stirred suspension of AlCl^.
The reaction was quenched after 1.25 hr by the addition of saturated
NH^Cl (20 mL). After allowing the mixture to warm to room temperature,
the organic phase was washed with saturated NH^Cl (2x20 mL), saturated
NaCl (2x20 mL), deionized H20 (2x20 mL), and dried over MgSO^. The
solvent was removed in vacuo leaving a yellow-brown oily residue which
was fractionated on a 2 mm silica gel TLC plate (5% Et20/hexane).
Isolated from the plate as colorless oils were alkenes 3£ (106 mg, 17%,
Rf 0.45) and 36 (15 mg, 2.5%, Rf 0.71). All spectral data (vide infra)
were consistent with their proposed structures.
Method B: AlCl3/Et20, 0C.
Typically to a flame dried 100 mL flask fitted with a septum, mag
netic stir bar, and N2 inlet, A1C13 (1.0 g, 7.5 mmole) was added. After
flushing with N3 anhydrous Et20 (40 mL) was added via syringe, and the


72
mixture was stirred at 0C for 10 min (until AlCl^ dissolved). To the
stirred solution of AlCl^, 7,7-dimethoxynorbornene (30, 1.0 mL,
6.6 mmole) was added dropwise via syringe and allowed to stir for an addi
tional 5 min. Next TMS-cyclopentadiene (28, 1.1 mL, 0.89 g, 6.5 mmole)
was added dropwise via syringe. The solution turned light brown after
the addition of the silane. After 3-4 hr, the solution turned very dark
(almost black), and the reaction was quenched by the addition of
saturated NH^Cl (40 mL). The organic phase was separated, washed again
with saturated NH^Cl (2x40 mL), and subsequently dried over MgSO^. The
solvent was removed in vacuo and a brown oil recovered (1.3 g). After
flash chromatography on silica gel (3% Et2/pentane) and further
purification on 1 mm prep TLC, relatively pure 26_ was obtained (15-20%
yield).
Method C: BF^*Et20/CH2CH2, 25C.
To a solution of TMS-cyclopentadiene (2 mL), 1.62 g, 11.7 mmole) in
CH2CI2 (25 mL, dried over 3 A sieves), freshly distilled BF2*Et20 (1 mL,
7.9 mmole) was added. There was an immediate yellow color upon mixing.
To this mixture, 7,7-dimethoxynorbornene (1 mL, 1.02 g, 6.6 mmole) was
added dropwise. The reaction was quenched after 1.75 hr by the addition
of 25 mL saturated NaHCO^g^. After separating the phases, the organic
layer was washed twice with brine and dried over MgSO^. The methylene
chloride was removed in vacuo leaving a yellow oily residue. Capillary
GC-MS analysis of the crude oil indicated at least three C-^^jgO isomers
with approximately 45% of the mixture to be 26_, with 5% as _39_, and 8%
to be _38. Fractionation of the crude reaction oil by flash
chromatography on silica gel (5% Et20/pentane) afforded a mixture of
C10H.^0 isomers in 29% yield.
13 lo J


73
Method D: BF3Et20/CH2Cl2, 5C.
To a 100 mL 3-neck flask fitted with a magnetic stir bar, thermom
eter, dropping funnel, N2 inlet, and septum was added a solution of
TMS-cyclopentadiene (_28^, 8.97 g, 65.0 mmole) in CH2C12 (25 mL, dried
O
over 3 A molecular sieves). After cooling the solution to 5C (ice/water
bath), BF3*Et20 (4 mL, 32.0 mmole) was added via syringe. To the stirred
mixture a solution of ketal _30 (5.0 g, 32.0 mmole, in 25 mL CH2C12 was
added dropwise over a 20 min period, while maintaining the temperature
S5C. After a total reaction time of 1.5 hr at 25C, the reaction was
quenched by the careful addition of saturated NaHCO^ (20 mL). The
organic phase was separated and then washed with NaliCO^ (2x20 mL), satu
rated NaCl (2x20 mL), and dried over MgSO^. After solvent removal in
vacuo, a yellow oil v/as recovered (7.9 g) which was immediately fraction
ated by flash chromatography to afford a mixture of isomers _26, _39 and _38
in 55.8% yield (see Table 5.1 for a summary of results). In other experi
ments employing Method D, the oily residue was left to stand for a short
period (overnight, 5-10C). The addition of pentane to the oily residue
(6.91 g) produced a precipitate, which was filtered to afford a pale
yellow solid (1.66 g). This precipitate was seemingly polymeric in
nature, as evidenced by a broadened NMR spectrum, and contained a
large percentage of trimethylsilyl moieties.
Spectral Data for Isolated Products from the Reaction of 7,7-Dimethoxy-
norbornene (30) with 5-Trimethylsilylcyclopentadiene (28) (Methods A-D)
7-Norbornylfulvalene (36)
The NMR spectrum (CDCl^, 60 MHz) contained the following
resonances: 66.35(m,6H), 3.5(m,2H), 1.9-l(m,4H).


Table 5.1. Method D: Fractionation by Flash Chromatography Correlated with
GC Retention Times and Area Percent
28
36
37
26
40
38
39
Fraction
Number
Weight (% Yield)
(1.37 min)
(4.55 min)
(4.87 min)
(5.06 min)
(5.11 min)
(5.19 min)
(5.26 min)
Crude
7.9 g (-)
27.9%
2.5%
3.4%
48.9%
0.35%
4.5%
8.0%
2b
2.11 g (23% rec)
86%
3.3%
-
-
-
-
-
4-5b
(polymerized on
_
30.4%
_
_
standing)
ioc
(trace)
-
-
-
13.0%
-
-
71.4%
11C
2.51 g (41.7%)
-
-
-
73.6%
-
3.1%
17.1%
12C
0.85 g (14.1%)
-
-
-
75.9%
0.12%
15.7%
1.9%
13d
(trace)
-
-
45.2%
17.9%
23.1%
5.4 %
-
14d
0.28 g (4.7%)
-

69.9%
0.9%

_
a GC conditions 80C (1 min) to 150C at 20C/min
b Pentane
c 5% Et90/pentane
d 10% Et^O/pentane


75
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 7 resonances: 6 168.33(s), 135.44(d), 130.70(d), 125.15(s),
121.39(d), 43.42(d), 23.93(t).
The mass spectrum (70 eV) had m/z (% rel intensity): 156(M+,49),
141(22), 128(100), 115(23), 102(11), 91(7), 78(12), 77(11).
syn-7-Methoxy-7-(1l-cyclopentadienyl)norbornene (37a) and syn-7-methoxy-
7-(1l-cyclopentadienyl)norbornene (37b), ca. (50:50)
The NMR spectrum (CDCl^ 60 MHz) contained the following
resonances: <5 6.42(mult,6H),6.09(t, J=1.7 Hz, 4H), 3.06(m,2H),
2.97(m,2H), 2.95(s,3H), 2.90(s,3H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 19 resonances: 145.43(s), 144.11(s), 135.39(d), 133.24(d),
132.71(d), 132.51(d), 132.02(d), 131.20(d), 130.56(d), 129.59(d),
96.01(s), 52.83(q), 52.63(q), 46.88(d), 46.44(d), 41.33(d), 39.72(d),
22.90(f), 22.80(f).
The mass spectrum (70 eV) had m/z (% rel intensity): 188(M+,59),
187(18), 173(20), 160(19), 159(36), 158(11), 157(36), 156(49), 155(44),
154(7), 153(11), 147(35), 145(25), 143(10), 142(18), 141(42), 134(14),
130(17), 129(55), 128(72), 127(19), 123(15), 115(55), 93(50), 91(88),
65(100).
Accurate mass of CloH.,0:
13 io
Caled 188.1201 amu
Found 188.1192 amu
3b-Methoxy-3a,3b,4,6a,7,7a-octahydro-3,4,7-metheno-3H-cyclopenta a 1pen-
talene (26)
The Hi NMR spectrum (CDCl^, 60 MHz) contained the following
resonances: 5.8(t, J=1.9 Hz, 2H), 3.3(s,3H), 2.9(m,2H), 2.64(pent,
J=2.95 Hz, 1H), 2.5(m,2K), 1.7(br s,4H), 1.47(d, J=2.74 Hz, 2H).


76
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 8 resonances: 130.36(d), 94.39(s), 62.96(d), 56.43(d),
55.94(d), 54.29(q), 43.96(d), 23.49(t).
The mass spectrum (70 eV) had m/z (% rel intensity): 188(M+,100),
173(10), 160(28), 145(21), 123(91), 108(61), 91(60), 77(30), 65(44).
Accurate mass of C.H,,0:
13 16
Caled 188.1201 amu
Found 188.12680.0009 amu
8-Methoxy-3a,3b,4,6a,7,7a-octahydro-3,4,7-metheno-3H-cyclopenta\a 1pen-
talene (38) (mixture with 26)
The NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: 6 5.96(d,d,d; J=6.0, 2.9, 0.86 Hz, HI), 5.79(mult,2H),
5.76(d,d; J=2.9, 0.85; 1H), 3.27(s,3H), 3.23(s,3H), 2.87(mult,2H),
2.70(mult,2H), 2.65(mult,1H), 2.48(m,2H), 2.0-1.2(mult).
13
The proton decoupled C NMR spectrum (CDCl^) contained the follow
ing 13 resonances (after subtraction of peaks for 26): 137.04(d),
129.64(d), 93.57(s), 52.97(q), 50.90(d), 494.22(d), 47.81(d), 45.66(d),
42.30(d), 39.47(d), 39.08(d), 26.02(t), 24.51(f).
The mass spectrum (70 eV) had m/z (% rel intensity): 189(14), 188(M+,
100), 173(14), 160(42), 159(22), 145(41), 129(24), 128(28), 123(68), 122(19),
121(27), 117(21), 115(29), 109(20), 108(45), 95(42), 93(23), 91(69), 79(29),
78(18), 77(33), 67(17), 65(43), 51(20), 45(30), 41(26), 39(41).
Accurate mass of C1oH..,0:
13 16
Caled 188.1201 amu
Found 188.12330.002 amu
3b-Methoxy-2,3,3a,3b,4,5,6,6a,7,7a-octahyd ro-1,4,7-metheno-lH-cyclo-
pentaTalpentalene (39)
The '''H NMR spectrum (CDC1, 60 MHz) contained the following
resonances: 6 6.3(d,d;J=2.6, 5.6 Hz; IK), 5.6(d,d; J=2.2, 5.6 Hz, 1H),
3.3(s,3H), 2.9(mult,2H), 2.5-1.0(mult,511).


77
13
The proton decoupled ~C NMR spectrum (CDCl^) contained the
following 13 resonances: 6 137.04(d), 129.64(d), 93.57(s), 52.97(q),
50.90(d), 49.22(d), 47.81(d), 45.66(d), 42.30(d), 39.47(d), 39.08(d),
26.02(t), 24.51(t).
The mass spectrum (70 eV) had m/z (% rel intensity): 188(M+,100),
173(13.6), 160(41.8), 145(40.9), 123(67.7), 109(19.7), 108(44.8),
95(42.4), 91(69.1), 77(32.6), 65(43.0).
Accurate mass of C.-H.^O:
13 lo
Caled 188.1201 amu
Found 188.12330.002 amu
Preparation of 3b-Methoxy-2,3,3a,3b,4,5,6,6a,7,7a-decahydro-l,4,7-
metheno-lH-cyclopenta[a]pentalene ( 39-112 )
To a standard hydrogenation apparatus was added 25 mL ethyl acetate
and 5 mg 10% Pd-C. The suspension was allowed to equilibrate with stir
ring under 1 atm of and a solution of alkene 39_ (61 mg, 0.32 mmole,
in 10 mL ethyl acetate) was added. The reaction was allowed to stir for
4 hr during which time 5.8 mL of 1^ was consumed. The reaction mixture
was filtered through celite, the solvent removed in vacuo, and a color
less oil recovered (57 mg, 94% yield). The and ^ C NMR indicated
complete reduction of the double bond.
The NMR spectrum (CDCl^, 60 MHz) contained the following
resonances: 6 3.2(s,3H,-0Me), 2.9-0.5(br m,15H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 13 resonances: 95.08(s), 51.90(q), 46.05(d), 44.79(d),
42.97(d), 42.25(d), 42.15(d), 41.67(d), 40.50(d), 28.36(t), 27.78(t),
27.34(t), 23.10(t).


78
Bromination of Methoxybisesquinene (26)
Preparation of trans-1,2-dibromo-3b-methoxy-3a,3b,4,6a,7,7a-decahydro-
3,4,7-metheno-3H-cyclopenta[a]pentalene (26-Br^)
To a flame dried flask, fitted with a rubber septum, ^ inlet, and a
magnetic stir bar, was added a solution of the crude Cj^^O isomer
mixture (405.6 mg, 2.15 mmole) in 10 mL methylene chloride and cooled to
-78C. A 10% (v/v) B^/Cl^C^ solution was added dropwise via syringe,
while stirring, until a faint orange color persisted. The flask was
removed from the cold bath and allowed to warm to room temperature while
stirring. The solvent was removed in vacuo, and a reddish oil was recov
ered (850 mg). Gas chromatographic analysis indicated two major compo
nents with retention times of 8.65 min (75.3%), 9.58 min (9.6%), which
were the trans-dibromide 26-Br^ and rearranged dibromide 43^, respec
tively. Flash chromatography on silica gel (5% Et20/pentane) afforded
the pure trans-dibromide 26_-Br2 as a white solid (433 mg, 57% yield,
mp 98-100C) which gave the following spectral data.
The NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: 4.53(d,d; J-2.7, J=5.2 Hz, 1H), 4.19(d, J=2.7 Hz, 1H),
3.30(s,3H), 2.85(pent, J=2.7 Hz, 1H), 2.60(mult,2H), 2.20(mult,2H),
2.05(mult,lH), 1.65(mult,4H).
13
The proton decoupled C NMR spectrum (CDC1Q) contained the
following 13 resonances: 6 96.98, 59.94, 58.33, 58.04, 56.33, 54.78,
53.61, 52.58, 48.69, 44.20, 40.84, 23.10, 22.80
The Mass spectrum (70 eV) had m/z: 348(M+,0.3), 270(14), 269(98),
268(15), 267(100), 237(12), 189(19), 188(58), 187(61), 173(13), 160(15),
159(22), 157(35), 156(34), 155(78), 145(23), 129(36), 128(29), 123(55),


79
121(28), 115(36), 109(33), 108(39), 97(28), 95(25), 93(24), 91(76),
82(49), 80(52), 79(45), 77(38), 71(58), 65(41), 57(35), 55(36), 41(34).
79 79 81
Accurate mass of: C1QH1;0 Br CloH.0 or Br
13 16 2 13 16
Caled 345.9568 amu 347.9547 amu
Found 345.95600.0053 amu 347.95490.0077 amu
Anal. Caled.
for C^H^B^O
%C
%H
Caled
44.86
4.63
Found
44.94
4.68
Preparation of exo,exo-l,3-dibromo-3b-methoxy-3a,3b,4,6a,7,7a-
decahydro-2,4,7-metheno-lH-cyclopentara]pentalene (43)
Bromination of the C^H^O isomer mixture (54.1 mg) at room
temperature produced a mixture of dibromides (82:18, 26-Br^, and 43,
respectively) which were separated by flash chromatography to afford the
rearranged dibromide 43_ as a colorless oil (33 mg, 33% yield) and 26-Brp
(45 mg, 45% yield). Spectral data for the rearranged dibromide 43 is as
follows.
The NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: 5 4.85(t, J=1.2 Hz, 1H), 4.08(t, J=1.46 Hz, 1H), 3.32(s,3H),
2.85(mult,2H), 2.70(mult,1H), 2.20(d, J=4.5 Hz, 1H), 2.10(d, J=3.0 Hz,
1H), 1.9-0.9(mult,6H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 12 resonances: 698.44(s), 54.43(d), 53.46(q), 51.32(d),
50.97(d), 48.25(d), 45.81(2 peaks?, d), 43.47(d), 42.50(d), 41.52(d),
24.12(t), 22.95(f).
The infrared spectrum (film) contained the following absorption
bands: 2950, 1465, 1300, 1250, 1110, 1025, 1005, 906, 835.
The mass spectrum (70 eV) had m/z (% rel intensity): 348(M+,0.59),
270(14), 269(97), 268(15), 267(100), 189(9), 188(21), 187(36), 159(13),


80
156(30), 155(63), 145(11), 129(27), 128(22), 123(55), 121(14), 117(13),
115(28), 109(17), 108(18), 93(15), 91(85), 79(44), 78(22), 77(41),
71(74), 66(11), 65(53), 51(26), 45(46), 41(36), 39(60).
Accurate mass of C^H^O^^Br^^Br:
Caled 347.9548 amu
Found 347.96420.0134 amu
Debromination of 26-6^
The dibromide 26-Br^ (843 mg, 2.42 mmole) was added to a 50 mL
flask and was dissolved with gentle heating in absolute ethanol (30 mL).
To this solution Zn dust (0.5 g, 7.65 mmole) was added followed by
5 drops of glacial acetic acid. The flask was stoppered and immersed in
a warm (50C) sonicator cleaning bath (Bransonic 220) for 7 min. A GC
aliquot indicated complete loss of 26-Br^. The Zn powder was removed by
filtration through celite, and the solvent was removed in vacuo. The
oily residue was dissolved in pentane, washed with saturated NaHCO^, and
filtered again to remove a white precipitate (ZnCO^?). The pentane was
removed in vacuo to produce pure 26_ (>99% by GC) in quantitative yield.
Reaction of 26 with Trimethylsilyl Iodide (TMS-I)
An oven-dried NMR tube was fitted with a septum and flushed with
argon. A solution of 26_ (+ isomers) (17 mg, 0.09 mmole) in CDCl^
(0.5 mL, dried over 3 K molecular sieves) was added. To this solution
trimethylsilyl iodide (25 pL, 0.18 mmole) was added via syringe. The
sample was incubated 24 hr at 40C in a thermostated oil bath, and the
reaction was monitored by NMR. After the incubation period, the most
noticeable change in the NMR was the appearance of a new -OMe peak at


81
3.3 ppm. The reaction was quenched by the addition of 2 drops of
methanol saturated with NaHCO^. The solvent was removed in vacuo, and
the residue was taken up in ether. The ether phase was washed with 5%
NaHSO^ (3x5 mL), saturated NaCl (3x5 mL), and dried over MgSO^. The
solution was filtered, the solvent removed in vacuo, and redissolved in
CDC13. Analysis by GC-MS [3% SP2100, 5 ft x 1/4 in, 100C (2 min) to
300C at 7C/min] indicated a mixture of at least 6 components.
Following are the values for the retention times, % relative peak height,
apparent M+, and suggested structures: 11.23 min, 6%, M+ 188, (26);
11.68 min, 24%, M+ 188, (39); 12.97 min, 12%, M+ 174 (hydroxybises-
quinene?); 15.4 min, 6%, M+ 220, unknown?; 19.18 min, 100%, M+ (not
visible), 316-127 = 189 (100%) (26-1); 14.8 min, 8%, M+ 332,
C13H16(188) + I(127) + 0H(17) = C13H1702I(332).
The major component (26-1) of this mixture was collected by
preparative GC and its structure determined by NMR and MS.
The NMR spectrum (CDC13, 100 MHz) contained the following
resonances: 6 4.7(mult,1H), 6.9 (s,3H), 2.5-1.0(mult).
The mass spectrum (70 eV) had m/z (% rel intensity): (M+ not
visible), 190(12), 189(M+-I,100), 188(11), 157(16), 142(21), 129(16),
128(16), 127(18), 123(30), 117(15), 115(15), 109(60), 108(25), 105(12),
91(49), 80(23), 79(64), 78(18), 77(33), 71(17), 67(20), 66(22), 65(26),
53(13), 51(16), 45(19), 41(31), 39(44), 32(14).
Preparation of exo-1,2-Epoxy-3b-methoxy-3a,3b,4,6a,7,7a-decahydro-3,4,7-
metheno-3H-cyclopenta^ alpentalene (67)
Typically, a CH2C12 solution (10 mL) containing alkene 26_ (193 mg,
1.06 mmole) was cooled to 0C and treated with Na2C03 (400 mg, 4 mmole),
purified mCPBA (276 mg, 1.6 mmole) and stirred for 2 hr. After addition


82
of 50 mL pentane, the mixture was washed with 10% NaHSO^ (4x50 mL), 10%
NaHCOg (4x50 mL), saturated NaCl (2x50 mL), and dried over Na2S0^.
Removal of the solvent in vacuo afforded a pale yellow oil (187.6 mg, 87%
yield, 94% pure by GC). The material was further purified by flash
chromatography on silica gel (10% Et20/pentane).
The ^H NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: 6 3.29(s,3H), 3.24(s,2H), 2.68(d, J=3.2 Hz, 2H),
2.25(mult,2H), 2.04(pent, J=3.1 Hz, 1H), 1.65(mult,6H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 8 resonances: 94.74(s), 54.48(q), 53.17(d), 51.66(d),
50.29(d), 42.89(d), 39.08(d), 23.24(t).
The mass spectrum (70 eV) had m/z (% rel intensity): 204(M+,69),
189(12), 188(14), 176(17), 175(61), 173(24), 161(23), 148(34), 147(36),
129(33), 128(38), 124(91), 123(68), 121(39), 117(37), 115(34), 109(63),
108(38), 98(48), 97(90), 96(39), 91(100), 81(61), 79(66), 77(55),67(45),
65(43), 55(42), 45(50), 41(52).
Accurate mass of C,H..,0:
13 16 2
Caled 204.1150 amu
Found 204.11480.0028 amu
Preparation of exo-l-Hydroxy-3b-methoxy-3a,3b,4,6a,7,7a-decahydro-3,4,7-
metheno-3H-cyclopentafalpentalene (64-0H)
In a typical reaction, epoxide 67_ (157.3 mg, 0.771 mmole) was added
in a pentane solution (15 mL) to a flame dried flask fitted with a septum
and a magnetic stir bar. The flask was flushed with argon, cooled to
0C, and DIBAL-H (1.6 mL, 1.5 mmole, 1 M in hexane) was added via
syringe. After stirring for 1 hr at 0C, the reaction was quenched by
addition of 15 mL MeOH. The gelatinous aluminum salts were removed by


83
filtration through celite and washed with hot MeOH (3x10 mL). The com
bined methanol washings were removed in vacuo and the residue was redis
solved in 10% Et20/pentane. Initial clean-up was accomplished by flash
chromatography on a short silica gel column (1 in) eluted with 400 mL 10%
Et20/pentane, 100 mL 10% MeOH/pentane, and 100 mL 20% MeOH/pentane, with
the product eluting in the final fraction. Removal of the solvent in
vacuo produced a colorless oil (124.7 mg, 78.5% yield, 96% pure by GC).
Further purification was achieved by flash chromatography on silica gel,
eluted with 50% EtOAc/pentane.
The NMR spectrum (CDCl^, 100 MHz) contained the following reso
nances: 3.94(dd,J=2.4 Hz, 7.1 Hz), 3.35(s,3H), 2.58(pent, J=2.9 Hz,
1H), 2.34(mult,2H), 2.22(s,2H), 2.1-1.3(mult).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 12 resonances: 696.84(s), 71.40(d), 59.41(d), 54.53(q),
53.22(d,2 peaks?), 50.19(d) 46.64(d), 43.81(d), 41.33(d), 37.67(t),
23.24(f), 22.85(f).
The mass spectrum (70 eV) had m/z (% rel intensity): 206(M+,17),
188(3.4), 163(15), 162(100), 147(18), 134(10), 131(39), 130(24), 123(24),
121(18), 109(26), 97(20), 96(34), 91(35), 79(19), 67(17), 65(14), 49(20),
41(25).
Accurate mass of
Caled 206.1307 amu
Found 206.12930.0026 amu
Preparation of exo-l-3b-Methoxy-3a,3b,4,6a,7,7a-decahydro-3,4,7-metheno-
3H-cyclopenta[alpentalene Acetate (64-OAc)
In a typical experiment, Et^N (49 yL, 2 equiv) and AC2O (18.4 yL,
1.1 equiv) were added to 64-0H (36.4 mg, 0.177 mmole) dissolved in


84
G^C^ (2 mL). The reaction was stirred for 10 min at room temperature,
and an aliquot analyzed on the GC indicated no reaction. Addition of
DMAP (1.08 mg, 0.05 equiv) and stirring for 3 hr afforded nearly complete
conversion of the alcohol to the acetate, as indicated by GC. After
solvent removal in vacuo, the residue was dissolved in 5 mL Et20 and
washed with 5% v/v HC1 (3x5 mL), saturated NaCl (3x5 mL) and dried over
MgSO^. Removal of the solvent in vacuo afforded a colorless oil (34.9 mg,
80% yield, 92.8% pure by GC). Further purification was effected by prep
TLC (10% Et?0/pentane) to finally recover 64-0Ac (30.5 mg, 70% yield,
97% pure by GC).
The NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: 6 4.80(dd, J=2.6 Hz, J=7.3 Hz, 1H), 3.35(s,3H), 2.55(pent,
J=2.3 Hz, 1H), 2.42(mult,2H), 2.23(mult,2H), 2.01(s,3H),
1.8-1.4(mult,7H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 14 resonances: 6 170.58(s), 96.64(s), 74.56(d), 55.95(d),
54.53(q), 53.27(d), 50.00(d), 47.37(d), 43.81(d), 41.28(d), 34.84(t),
23.15(f), 22.76(f), 21.30(q).
The mass spectrum (70 eV) had m/z (% rel intensity): 248(M+,11.9),
189(31.6), 188(67.0), 162(62.4), 123(36.4), 109(56.1), 108(30.0),
91(41.2), 84(38.9), 79(29.4), 51(28.4), 49(66.1), 43(100), 41(33.0).
Accurate mass of
Caled 248.1412 amu
Found 248.14120.0028 amu
Preparation of 1l-Keto-tetracyclo[6.2.1.1^^.0"^ldodec-4-ene (66)
To a flame dried flask alcohol (127.5 mg, 0.72 mmole) and
CrO^ 2pyr (0.94 g, 3.6 mmole) were added and fitted with a magnetic stir


85
bar and a septum. The flask was flushed with argon and dry pyridine
(5 mL) was added via syringe. After stirring for 1.5 hr, an aliquot on
GC indicated complete reaction. The pyridine solution was poured into
50 mL H2O and extracted with pentane (3x20 mL). The combined pentane
extracts were washed with 10% HC1 (3x25 mL), saturated NaHCO^ (25 mL),
H2O (25 mL), and dried over MgSO^. Removal of the solvent in vacuo
afforded a white solid (120 mg, 95.7% yield, 95% pure by GC). Recrystal
lization from pentane gave a white solid (mp 53-57C, 99% pure by GC).
The ^H NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: 6 5.98(t, J=1.7 Hz, 2H), 2.9(mult,2H), 2.2(mult,2H),
1.8-0.6(mult,8H).
13
The proton decoupled C NMR spectrum (CDC10) contained the
following 7 resonances: 6 216.06(s), 136.61(d), 49.15(f), 48.88(d),
45.12(d), 42.13(d), 22.53(f).
Preparation of anti-11-Methoxy-tetracyclof6.2.1.1~^^.0^^ldodec-4-ene (72)
To a flame dried flask transferred to a dry box, alcohol 7_1 (200 mg,
1.14 mmole) and dry NaH (55 mg, 2.3 mmole) were added. The flask was
fitted with a magnetic stir bar and a septum and cooled to -78C in a dry
ice bath. Dry THF (20 mL) v/as slowly added via syringe to the cold flask
was allowed to stir 1-2 min after which the flask was allowed to warm to
room temperature. Freshly distilled Mel (143 yL, 2.3 mmole) was then
added via syringe, and the mixture was stirred overnight. The contents
of the flask were poured onto ice/H?0 and extracted with ether. After
drying over I'^SO^, the solvent was removed in vacuo to yield a colorless
oil (212.4 mg, 98% yield).


87
The mass spectrum (70 eV) had m/z (% rel intensity): 206(M',4.8),
149(86.5), 123(20.6), 117(39.2), 109(41.4), 93(48.8), 92(43.3),
91(81.7), 82(43.7), 81(63.0), 79(67.0), 77(40.8), 71(100.0), 67(51.9),
66(44.2), 45(73.2), 41(99.3), 39(59.3).
Accurate mass of
Caled 206.1307 amu
Found 206.12990.0024 amu
Preparation of exo-3b-Methoxy-3a,3b,4,6a,7,7a-decahydro-2,4,7-metheno-lH-
cyclopenta[alpentalen-3-ol (65-0H)
To a flame dried flask, fitted with a stir bar, septum and purged
with N2 dry THF (15 mL) and freshly distilled Et(250 yL, 2.4 mmole)
were added. The solution was cooled to 0C, and n-butyl lithium
(1.5 mL, 1.7 mmole, 1.1 M in hexane) was added and stirred for 10 min.
A solution of epoxide 73. (105 mg, 0.52 mmole) in THF (5 mL) was added
via syringe, the solution was refluxed overnight, and then stirred at
room temperature for 7 days. The brown solution was diluted with 20 mL
H2O, then extracted with Et?0 (2x20 mL). The combined Et20 extracts
were washed with saturated NaCl (2x20 mL), dried over h^SO^, and the
solvent removed in vacuo. After flash chromatography on silica gel (2%
MeOH/C^C^ then 4% MeOH/C^C^), a yellowish oil was recovered (57 mg,
53% yield).
The NMR spectrum (CDCl^, 60 MHz) contained the following
resonances: 54.3(d, J=2.4 Hz, 1H), 3.3(s,3H), 2.6-0.9(mult,13H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 12 resonances: 5 95.62(s), 73.25(a), 53.92(q), 48.73(d),
44.84(d, 2 peaks?), 44.54(d), 43.18(d), 41.28(d), 40.30(d), 31.30(t),
25.24( t), 22.41(t).


88
The mass spectrum (70 eV) had m/z (% rel intensity): 206(M ,3),
150(11), 149(100), 125(22), 124(4), 123(1), 117(14), 109(5), 97(4),
91(12), 79(6), 67(5), 66(2), 65(3), 55(3), 53(4), 45(4), 41(8), 39(5).
Accurate mass of C^2^g02:
Caled 206.1307 amu
Found 206.13060.0014 amu
Preparation of 3b-Methoxy-3a,3b,4,6a,7,7a-decahydro-3,4,7-metheno-3H-
cyclopenta[a]pentalene (26-^)
A standard atmospheric hydrogenation apparatus was charged with 20 mL
EtOAc and 50 mg 10% Pd-C. After the stirred suspension was allowed to
equilibrate under 1 atm 1a solution of 26_ (500 pL, 543 mg, 2.87 mmole
in 10 mL EtOAc) was added. After stirring for 40 min approximately 60 mL
of H2 was consumed. The reaction mixture was filtered through celite, and
the solvent was removed in vacuo to give a colorless oil in quantitative
yield (91% pure by GC). The reduced material was used without further
purification for the next step (reaction with TMS-iodide).
The NMR spectrum (CDClg, 60 MHz) contained the following
resonances: 6 3.4(s,3H); 2.26-2.15(mult,5H); 1.56-1.50(mult,1H).
13
The proton decoupled C NMR spectrum (CDClg) contained the
following 8 resonances: 0 96.93, 54.29, 53.17, 51.36, 48.88, 45.18,
25.05, 23.10.
The mass spectrum (70 eV) had m/z (% rel intensity): 191(M+,46.0),
189(88.8), 188(12.9), 162(45.8), 129(43.1), 123(69.2), 109(100),
96(63.3), 95(53.5), 91(97.4), 81(40.5), 30(39.2), 79(85.8), 77(57.8),
67(75.2), 65(41.0), 55(45.0), 41(78.8), 39(64.1).
Accurate mass of C-^H^gO:
Caled
Found
190.1358 amu
190.134810.0019 amu


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81,9(56,7< 2) )/25,'$ ,QL QL LQQ LLLQ HIW


UNIVERSITY OF FLORIDA
Ini ni inn iiin eft7
3 1262 08556 7567


SYNTHESIS AND CHEMISTRY OF
3,4,7-METHENO-3H-CYCLOPENTA[A]PENTALENES
(BISESQUINANES)
BY
BILLY GLYNN GRIGGS, JR.
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
1985

IN MEMORY OF MY GRANDFATHER
who spent 40 years as a high school
teacher of chemistry, math and physics
and instilled in me a love of science

ACKNOWLEDGEMENTS
The author would like to express his gratitude to
Professor M. A. Battiste for his guidance throughout the course of this
work; his willingness to be interrupted to discuss new results or just to
chat was a joy. In his role as academic advisor, Dr. Battiste has helped
the author develop a sense of independence and maturity by knowing when
to offer help and when to leave him time to solve his own problems.
Special thanks are due to all of the author's friends who have
contributed a vital service of babysitting for the past few weeks.
Without their generous support, this manuscript v/ould never have been
completed.
Finally, to the author's typist and helpmate he says your loving
support, understanding of all the late nights in the lab, and eagerness
to help is appreciated beyond description. Your ability to take
everything in stride (almost, anyway) and maintain a semblance of order
in our household has qualified you as a Proverbs 31 woman. "An excellent
wife, who can find? For her worth is far above jewels. The heart of her
husband trusts in her, and he will have no lack of gain."
iii

TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
LIST OF TABLES viii
LIST OF FIGURES ix
ABSTRACT x
CHAPTER ONE INTRODUCTION 1
CHAPTER TWO SYNTHESIS OF METHOXYBISESQUINENE 7
Synthetic Strategy 7
Preparation of 7,7-Dimethoxynorbornene (30). 7
Preparation of 5-Trimethylsilylcyclopenta-
diene (28) 8
Reaction of 7,7,Dimethoxynorbornene with
Trimethylsilylcyclopentadiene 10
Structure Determination 11
Nuclear Magnetic Resonance 11
Mass Spectra 17
Mechanism 18
Improved Isolation of 26_ from Isomer Mixture 19
CHAPTER THREE REACTIVITY AND REARRANGEMENTS OF BISESOUINENE. ... 22
Acid Catalyzed Rearrangements in Metnoxybises-
quinene 23
Addition Reactions of the Double Bond 25
Preparation of Acid Rearrangement Products ... 28
Results of Acid Addition to the Double Bond of
Methoxybisesquinene (26) 30
Conclusions 36
IV

Page
CHAPTER FOUR STRAIN AND STRUCTURAL EFFECTS IN THE BESESQUINANE
SYSTEM 37
Strain Energy 37
MM2 Calculations 37
Homoketonization 41
Bisesquinane Structure: Calculated and X-Ray. . 47
Bond Lengths 47
Bond Angles 51
13
C-H Spin-Spin Coupling and Angle Strain. . 55
Interplanar Angles 56
Diels-Alder Reactivity of Bisesquinene:
Adduct Stereochemistry 58
Preparation of Adducts 61
Stereochemistry 62
Suggestions for Future Work 66
CHAPTER FIVE EXPERIMENTAL 67
General 67
Synthesis 69
Preparation of 7,7-Dimethoxynorbornene (30). 69
Preparation of 5-Trimethylsilylcyclopen-
tadiene (28) 70
Reaction of 7,7-Dimethoxynorbornene (30)
with 5-Trimethylsilylcyclopentadiene (28). . 71
Method A: A1C13/CH2C12, -78?C 71
Method B: AlCl3/Et20, 0?C 71
Method C: BF3 Et20/CH2CH2, 25?C .... 72
Method D: BF3 Et20/Ch’2Cl2, 5?C 73
Spectral Data for Isolated Products from
the Reaction of 7,7-Dimethoxy-norbornene
(30) with 5-Trimethylsilylcyclopentadiene
(28) (Methods A-D) 73
7-Norbornylfulvalene (36) 73
syn-7-Methoxy-7-(1’-cyclopentadienyl)-
norbornene (37a) and syn-7-methoxy-7-
(1'-cyclopentadienyl)norbornene (37b),
ca. (50:50) . 75
3b-Methoxy-3a,3b,4,6a,7,7a-octahydro-
3,4,7-netheno-3H-cyclopenta?a? pen-
talene (_26) 75
v

8-Methoxy-3a,3b,4,6a,7,7a-octahydro-
3,4,7-metheno-3H-cyclopenta[a]pen-
talene (38) 76
3b-Methoxy-2,3,3a,3b,4,5,6,6a,7,7a-
octahydro-1,4,7-metheno-lH-cyclo-
penta[a]pentalene (39) 76
Preparation of 3b-Methoxy-
2,3,3a,3b,4,5,6,6a,7,7a-decahydro-l,4,7-
metheno-lH-cyclopenta[a]pentalene
(39-H2) 77
Bromination of Methoxybisesquinene (26). . . 78
Preparation of trans-1,2-dibromo-3b-
methoxy-3a,3b,4,6a,7,7a-decahydro-
3.4.7-metheno-3H-cyclopenta[a]pen-
talene (26-BrQ 78
Preparation of exo,exo-l,3-dibromo-3b-
methoxy-3a,3b,4,6a,7,7a-decahydro-
2.4.7-metheno-lH-cyclopenta[a]pen-
talene (43) 79
Debromination of 26-Br^ 80
Reaction of 26_ with Trimethylsilyl Iodide
(TMS-I) 80
Preparation of exo-1,2-Epoxy-3b-methoxy-
3a,3b,4,6a,7,7a-d ecahyd ro-3,4,7-metheno-
3H-cyclopenta[a]pentalene (67) 81
Preparation of exo-l-Hydroxy-3b-methoxy-
3a,3b,4,6a,7,7a-decahydro-3,4,7-metheno-
3H-cyclopenta[a]pentalene (64-OH) 82
Preparation of exo-l-3b-Methoxy-
3a,3b,4,6a,7,7a-decahydro-3,4,7-metheno-3H-
cyclopenta[a]pentalene Acetate (64-OAc). . . 83
Preparation of 11-Keto-tetracyclo-
[6.2.1. l^’^.O^’^]dodec-4-ene (66) 84
Preparation of anti-ll-Methoxy-tetracyclo-
[6.2.1.13,6.02,7]dodec-4-ene (72) 85
Preparation of cis,anti-4,5-Epoxy-anti-
tetracyclo[6.2.1.I3’^.02’^]dodec-ll-
methyl Ether (73) 86
Preparation of exo-3b-Methoxy-
3a,3b,4,6a,7,7a-decahydro-2,4,7-metheno-
lH-cyclopenta[a]pentalen-3-ol (65-0H). ... 87
Preparation of 3b-Methoxy-3a,3b,4,6a,7,7a-
decahydro-3,4,7-metheno-3K-cyclopenta-
[a]pentalene (26-H^) 88
vx

Page
Preparation of 3b-Hydroxy-3a,3b,4,6a,7,7a-
decahydro-3,4,7-metheno-3H-cyclopenta-
[ajpentalene (96) 89
Preparation of Tetracyclo[7.2.1.0 .0 ]-
dodeca-l-one (98) 90
Reaction of 26. with Trifluoroacetic Acid
(TFA) 91
Preparation of Diels-Alder Adduct (103a) . . 92
Treatment of Adduct 103a with TMS-1 93
Preparation of Tetrachloroketone 108 .... 93
Reaction of Tetracyclone (104) with
Methoxybisesquinene (26) to Produce
Diels-Alder Adduct 105a and Diene 106. ... 95
Spectral data for 105a 95
Spectral data for 106 96
APPENDIX 1 Nomenclature and Derivation of Trivial Name
"Bisesquinane" 97
APPENDIX 2 Selected XH and 13C NMR Spectra 101
REFERENCES 135
BIOGRAPHICAL SKETCH 139
vi i

LIST OF TABLES
Table Page
2.1 Representative Results of Reaction between Ketal 3(3
and Silane 28^ under Various Conditions 12
3.1 Acid Catalyzed Rearrangement of Methoxybisesquinene _26 . . 31
4.1 MM2 Energy Calculation Results (kcal/mole) 40
4.2 Bond Lengths [Á] with Estimated Standard Deviations in
Parentheses for Dibromide 26-Br^ Involving Non-H Atoms . . 49
O
4.3 Bond Lengths [A] forDibromide 26-Br^ Involving H Atoms . . 50
4.4 Bond Angles [°] with Estimated Standard Deviations in
Parentheses for Dibromide 26-Br^ 53
4.5 Bond Angles [°] for Dibromide 26-8^ Involving H Atoms . . 54
5.1 Method D: Fractionation by Flash Chromatography
Correlated with GC Retention Times and Area Percent. ... 74
viii

LIST OF FIGURES
Figure Page
2.1 GC of reaction mixture showing identification of isomers . 13
2.2 Comparison of mass spectral fragmentation patterns for
compounds 36^ _37_, _26^ 38_ and _39 14
4.1 MM2 Calculations of strain energy. 38
4.2 INEPT 13C NMR spectrum of ketone 9É3 46
4.3 MM2 Calculated bond lengths for 4_, 80 and 81_ 48
4.4 Steroscopic view of the molecular structure of 26-Br^. . . 47
4.5 MM2 Calculated bond angles for 4_, 80 and ^ 52
4.6 Perspective drawings of bisesquinane (4^) 55
13
4.7 C-H Coupling constants for methoxybisesquinene (26)
and related bicyclic hydrocarbons 57
4.8 Crystal structure of 26-Br^ as viewed down the
C(5) —C(12) bond 58
4.9 Interplanar Angles 59
4.10 Carbonyl multiplicity 65
IX

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
SYNTHESIS AND CHEMISTRY OF
3,4,7-METHEN0-3H-CYCL0PENTA[A]PENTALENES
(BISESQUINANES)
By
Billy Glynn Griggs, Jr.
May 1985
Chairman: Dr. Merle A. Battiste
Major Department: Chemistry
An effective entry into the 3,4,7-metheno-3H-cyclopenta[a]pentalene
(bisesquinane) ring system was achieved via a novel tandem alkylation-
intramolecular [4+2] cycloaddition reaction. The addition of TMS-cyclo-
pentadiene to 5,5-dimethoxynorbornene in the presence of Lewis acid
catalysts produced 3b-methoxy-3a,3b,4,6a,7,7a-octahydro-3,4,7-metheno-3H-
cyclopenta[a]pentalene (methoxybisesquinene) as the major product in
addition to other C^H^O polycyclo-alkene isomers. A mechanism to
account for the isomeric products requires rearrangements via Tr-bond
bridging to an intermediate allyl silane cation. A simple purification
scheme via a bromination/debromination procedure was developed, thus
affording methoxybisesquinene in high purity in an overall three-step
process.
Addition reactions to methoxybisesquinene were quite facile and
under kinetic conditions gave predominantly exo addition products without
x

rearrangement. Under equilibrating conditions, Wagner-Meerwein skeletal
rearrangements occurred to produce predominantly 2,4,7-metheno-3H-cyclo-
penta[a]pentalenes (twist-methoxybisesquinenes). In no case was further
3 6 2 7
rearrangement observed to produce ll-keto-tetracyclo[6.2.1.1 ’ .0 ’ ]-
dodec-4-ene, the expected frangomeric cleavage product of the interme¬
diate twist-methoxybisesquinane cation. In fact, under acidic
conditions, this ketone was found to undergo homoconjugate addition to
produce a twist-bisesquinane diol.
The unusual chemistry of the bisesquinane system can be accounted
for by strain effects. Strain energies were calculated (MM2) for
bisesquinane and related systems to probe the effect of strain on
structure, bonding and reactivity. The calculated structural parameters
for bisesquinane are compared with those obtained from an x-ray crystal
structure of dibromomethoxybisesquinane. The two central bonds [C(10,ll)
and C(5,12)] are substantially longer than normal, implying that these
bonds are stretched as a consequence of strain. As predicted on the
basis of strain relief, homoketonization of bisesquinol produced a single
ketone. The highly compressed bridgehead bond angles of bisesquinane
contribute significantly to the strain energy and result in somewhat
larger coupling constants than related bicyclo-alkenes. The
structure of bisesquinane is unique compared to norbornane in that the
bridge methylenes are "tied back" by the central C(10)—C(11) bond, which
results in a much more open exo-face. The effects of these structural
perturbations and strain on the stereochemistry of Diels-Alder reactions
with dimethoxytetrachloro-cyclopentadiene and tetracyclone were
investigated.
xi

CHAPTER ONE
INTRODUCTION
It has long been the goal of the synthetic chemist to construct
complex molecules in as few steps as necessary to perform the task at
hand. Rapid construction of multiple rings is often required in the
elaboration of complex natural and unnatural products. With this in
view, many elegant methodologies have been utilized to construct a wide
variety of polycyclic hydrocarbons.
Multiple sequence Diels-Alder cycloaddition reactions are gaining
prominence as the methods of choice for ring construction steps. One
very useful approach is the intramolecular Diels-Alder reaction, where
after the coupling of diene with a reactive ene (via a single bond
formation), the molecule is then poised to react further via succeeding
Diels-Alder coupling.
This methodology also offers the advantages of a convergent synthesis,
whereby portions of the molecule can be formed independently, and finally
brought together at a later stage in the synthetic scheme. Other
examples of multiple sequence Diels-Alder cycloaddition have been called
"Domino"^ "Timed",^ "Tandem"^ and "Diene-Transmissive"^ Diels-Alder
reactions.
1

2
An interesting variation of this theme is the Domino Diels-Alder
reaction'*' which envokes a cascading sequence of [4+2] cycloadditions.
This may be described generally as an initial intermolecular [4+2] cyclo¬
addition, followed by intramolecular [4+2] bonding with the newly formed
olefinic center. This process is illustrated in structures Jh-_3, and
could be continued if structurally permissible.
The novel hydrocarbon skeleton "bisesquinane" (decahydro-
3,4,7-methenocyclopenta[aJpentalene, _4; see Appendix 1 for nomencla¬
ture discussion) has been prepared independently by Paquette and Wyvratt^
and McNeil et al.b utilizing the Domino Diels-Alder process. Their
synthesis formally requires the addition of acetylene to 9,10-dihydroful-
valene (_5) producing the intermediate 7-(5'-cyclopentadienyl)norborna-
diene (]3 ), which then undergoes rapid [4+2] cycloaddition to form
bisesquinadiene (_7).

3
In practice, a reactive dienophile, acetylene dicarboxylate (9),
was employed (Scheme 1.1) to produce a mixture of dicarboxylate cycload¬
ducts K) and H_. The isomeric mixture can be rationalized by the
approach of the dienophile (9) along coordinates a_ and Jd, respectively,
followed by the intramolecular [4+2] closure. Reduction, hydrolysis, and
oxidative decarboxylation of the minor isomer (11) afforded bisesquina-
diene (_7) in an overall yield of 7.3%.
Scheme 1.1
The research group of Paquette has recently completed the synthesis
of dodecahedrane (14), which had its genesis in the Domino Diels-Alder
reaction.^ This process allowed the multiple fusion of cyclopentane
rings conveniently and in good yield to produce the pentacyclic diester
10 which served as the "cornerstone" precursor of the elusive dodecahe¬
drane (14).

4
A key step in the synthesis involves cleavage of the central C-C bond,
which was facilitated by the high degree of ring strain in 10.
In view of the synthetic and theoretical interest of dodecahedrane
and its precursors, our group began exploration of alternate avenues
to polyfused cyclopentanoid systems. Synthesis of bisesquinadiene (_7) was
9
achieved by a novel approach we have termed a "tandem alkylation-[4+2]
cycloaddition." Essentially, this strategy requires the coupling of a
norbornadienyl cation (15) with a cyclopentadienyl anion (8) followed by
rapid intramolecular [4+2] cycloaddition of the intermediate 7-(5'-cyclo-
pentadienyl)norbornadiene (6_).
15 S_ 6_ _
For synthetic manipulation, this is most easily accomplished by the
in situ formation of these reactive species from 7-norbornadienyl
chloride (16) and thallium cyclopentadiene (TICp, 17) refluxed in dry
diglyme. Thus, as outlined in Scheme 1.2, bisesquinadiene (_7) was pre¬
pared in 8-12% yield by a convenient one-pot reaction from commercially
available starting materials.

5
Scheme 1.2
One of the major problems in this scheme is the formation of unde¬
sired side products. The 7-norbornadienyl cation-cyclopentadienyl anion
pair (18) can collapse at either C(7) or C(2) of the cation skeleton to pro¬
duce 6_ and the tricyclic hydrocarbon _19. After a series of sigmatropic
rearrangements, _19 produces a mixture of dihydro-as-indacenes (20-22).
Therefore, to improve on this methodology, one would need to increase
the charge density/localization at the 7-position of the norbornadienyl
cation (23) in order to prevent attack at C(2).
24 25
23

6
This may be accomplished by the introduction of an electron-donating
moiety at C-7 to localize the charge (e.g., _24_ => 25). The metnoxy group
has been shown to stabilize the incipient carbocation to such an extent
that participation by the double bond is relatively ineffective.^ ^
With these considerations in mind, our goal was to try to improve
this methodology to increase the yield of the reaction and to introduce
additional functionality. The target compound selected for study was
2a-methoxyoctahydro-3,4,7-methenocyclopenta[a_]pentalene (26), or more
simply, methoxybisesquinene (26). Its synthesis and reaction by-products
will be discussed in Chapter Two.
26
Methoxybisesquinene (26) offers many possibilities for mechanistic
study concerning the effect of ring strain and possible anchimeric assis¬
tance for thermal or acid catalyzed rearrangement. Also of interest is
the unusual reactivity of the double bond in addition reactions, and
these points will be addressed in Chapter Three.
The unusual chemistry of the bisesquinane system can be accounted
for in part due to its high ring strain. Molecular mechanics calcula¬
tions, an x-ray crystal structure, and a novel homoketonization experi¬
ment help to define the effects of this ring strain. In addition, the
facile participation of _26 as a dienophile in [4+2] cycloaddition
reactions and the questions of stereochemistry of the adducts will be
discussed in Chapter Four.

CHAPTER TWO
SYNTHESIS OF METHOXYBISESQUINENE
Synthetic Strategy
Utilizing a retrosynthetic analysis for methoxybisesquinene (26),
the application of an intramolecular Diels-Alder process preceded by. the
requisite alkylation is readily apparent.
Preparation of 7,7-Dimethoxynorbornene (30)
The synthetic equivalency of 7,7-dimethoxynorbornene (30) to oxonium
ion 29 is based upon the results of acidic hydrolysis of ketals in which
13
an oxo-carbonium ion is an assumed intermediate. Treatment of ketal 30
7

8
with a Lewis acid should provide the stabilized oxonium ion (29),
MeCL .OMe
v"e
Lewis
Acid
30
29
The ketal (30) is readily available from hexachlorocyclopentadiene (31)
via the three step reaction sequence illustrated in Scheme 2.1, as previ¬
ously described.^^
.Cl CH.OH 0MeCH_£^H2Cly-^Sl
Cl K0H A
MeOv^OMe MeO\/OMe
CL
CL
Eton
31
32
30
Scheme 2.1
Preparation of 5-Trimethylsilylcyclopentadiene (28)
The synthetic equivalence of 5-trimethylsilylcyclopentadiene (28)
for the cyclopentadienyl anion (£3) is perhaps less evident. There is by
now ample precedent for the reaction of allyl silanes with appropriate
electrophiles^ ^ in the presence of Lewis acids.
Nu-S¡R3 +

9
This reactivity has recently been extended to include additions to
ketals.^
OR
RO^
^=N/Sl"e3
RO.
*° oz
Lewis Acid
RO
OR
i
At the initiation of our studies, however, there was relatively little
information on this aspect of our synthesis. Even to date there have
been no reported analogous studies of the electrophilic alkylation of
28 with ketals.
Treatment of a tetrahydrofuran (THF) solution of cyclopentadiene
with sodium metal, or preferably sodium hydride, provides the rose-
colored sodium cyclopentadienyl anion (8_), which then reacts with
20
trimethylsilylchloride (TMS-C1) to generate silane 28.
8 28
A complicating property of 28_ is its facile rearrangement to isomers
34 and 35., presumably via 1,5-hydrogen shifts, but if the reaction
is kept cold (<20° C), essentially most of the material isolated is

10
21 22 21
isomer _28. ’ Ashe has reported an equilibrium ratio of 90:7:3 for
isomers _2<3, 34 and _35_, respectively, in which provides baseline
resolution of the NMR signals of the SiMe^ groups. In CDCl^,
isomers 34_ and _35 have identical SiMe^ chemical shifts, but isomer 28. is
23
resolved and is present to the extent of 87%. It may be noted that
this tendency of the trimethylsilyl group to favor substitution on the
5-position is remarkable compared to alkyl groups which seek out only the
1- and 2-positions. It has been reported that fractional crystalliza¬
tion by a successive partial freeze-thaw-filter technique affords pure _28
21
(mp -19°C). This method was found to be too tedious in our hands for
synthetic scale; therefore, the isomer mixture (28, 34 and 35) was used
directly with no apparent ill effects.
Reaction of 7,7-Dimethoxynorbornene
with Trimethylsilylcyclopentadiene
After translation, a relatively simple one-pot synthesis of
methoxybisesquinene (26) now appears
Scheme 2.2
The problem becomes to find the proper reaction conditions to favor the
coupling. This primarily depends upon the choice of Lewis acid, solvent,
and temperature.

11
The reaction was run under a variety of conditions utilizing various
Lewis acids and solvents (see Table 2.1). Surprisingly, upon capillary
GC-MS analysis, we observed not only _26 in the reaction mixture but at
least three other (C^g^gO) isomers (see Figures 2.1 and 2.2). The yield
and ratio of these various isomers were very dependent upon the reaction
conditions, particularly the nature of the Lewis acid and solvent.
Scheme 2.3 summarizes these results and shows the major isomers obtained
(26 or 39). In addition, most reaction methods were accompanied by the
formation of a yellow polymeric material, which was insoluble in pentane,
and contained a relatively large amount of trimethylsilyl residues.
Separation of the crude reaction mixture by flash chromatography on
silica gel afforded a mixture of four isomers (ca. 8-57% yield).
It was extremely difficult to resolve this isomer mixture, but by careful
flash chromatography followed by preparative TLC or GC, the major isomer
(26 or 39) could be obtained relatively pure (>95%).
Structure Determination
Nuclear Magnetic Resonance
Fulvalene 36 was isolated as a minor product in the best yield
(2.5%) from Method A. The symmetrical nature of fulvalene _36_ was readily

Table 2.1. Representative Results of Reaction between Ketal J30 and Silane ^8 under Various Conditions
Time
Isomer Ratio
Isolated
Yield
(Isomer
Method
Ketal 30
Silane 28
Lewis Acid
Solvent
Temp
(hr>
26 40? 38 39
Mixture)
A
500 mg
(3.25 mmole)
448 mg
(3.25 mmole)
A1C13
ch2ci2
-78°C
1.3
(not available)
17%
(39)
A
1.0 g
(6.5 mmole)
0.9 g
(6.5 mmole)
A1C13
cii2ci2
-78°C
1-2
14 2 10 63
8.7%
B
1.0 mL
(6.5 mmole)
0.9 g
(6.5 mmole)
A1C13
Et20
0°C
3-4
(not available)
15-20%
(26)
C
1.0 mL
(6.5 mmole)
2 mL
(11.7 mmole)
BF3-Et20
ch2ci2
25°C
1.75
77 - 8.8 14
29%
D
4.06 g
(26.3 mmole)
7.37 g
(53.4 mmole)
BF3*Et20
ch2ci2
5°C RT
3.3
78.9 - 8.2 12.9
57%
D
5.0 g
(32 mmole)
8.97 g
(65.0 mmole)
BF3*Et90
cii3ci2
0-5°C
1.5
79.2 0.6 7.3 13.0
55.8%

13
Figure 2.1. GC of reaction mixture (Method D) showing identification of
isomers.

14
Bise Peak = 128.0 Base Peak Abundance = 1664
li 1, ll 4t .1
36
* » i i i —t — —i — —i 1 i 1 i — -i i 1 | 1 —
50 100 150 200
F’-= k — li'S. u P•? ük ñbundctf'iC €' —
i
250
■ ~) —i —i —i —i —| —i~~i —i —i —|-
50 1Ü0 150 200 250
Base Peak = 188.1 Base Peak Abundance = 3464
, Li l.
li
- H “
1 00
.111 Jill
26
Base Peak = 188.1 Base
150 20©
Peak Abundance =
1--,-
25Ü
1 122
ll ,
L'l l. 1 i u It..1
1 M J
- -t
1 0 0
UiJii
150
39
'â–  M 0
1
:• =; m
MeO
108
173 (108)
Figure 2.2. Comparison of mass spectral fragmentation patterns for
compounds _36, _37_, 26_, _38^ 39.

15
13
apparent by inspection of its C NMR spectrum. At a short pulse delay,
the two quaternary vinyl carbon signals were missing, and only 5 signals
were observed: three vinyl carbons (=CH), one methyne (CH), and one
methylene (CT^). When the pulse delay was increased to allow for the
longer relaxation times (T^) of the quaternary carbons, 2 new peaks
appeared in the vinyl region. The NMR spectrum for 36_ was also
characteristically symmetrical with a complex vinyl multiplet (6 6.4, 6H)
bridgehead multiplet (6 3.5, 2H), and endo/exo ethylene multiplets
(6 2-1.2, 2H, 2H).
Isomer 37_ equilibrated to form a ca. 50:50 mixture of 37a and 37b
13
as evidenced by doubling of peaks in the C NMR spectrum, with four Cf^
i
peaks, two CH peaks, two -OMe peaks, one small quaternary -C-OMe peak,
and nine vinyl peaks. In the NMR spectrum, the vinyl region contained
a multiplet for the cyclopentadienyl residues (ca. ó 6.2, 6H) and a close
triplet (6 6.0, 4H) which is characteristic of symmetrical 7-substituted
norbornenes. Farther upfield appeared two -OMe signals superimposed on
two sets of bridgehead and cyclopentadienyl methylene multiplets (ca.
6 3, 12H), followed by two well-separated multiplets for the endo and exo
ethylene hydrogens (6 1.6, 4H and ó 0.9, 4H, respectively).
From mechanistic considerations, we could predict at least four
other isomers. To distinguish among these possibilities, we made
use of existing molecular symmetry and in some cases created symmetry for
spectral simplification. Scheme 2.4 outlines the symmetry results after
reduction of the double bond in compounds 26_, _38_, _39 and 40 with the
bracket numbers indicating the total number of carbon signals expected in
13
C NMR.

16
Scheme 2.4
The structure for 26_ was confirmed by its expected simple eight-
13 1
line C NMR spectrum (due to its symmetry), with one quaternary (-C-),
one vinyl (=CH), four methyne (-CH), one methylene QCl^), and one -OMe
signals. The ^H NMR spectrum of _26 was also characteristic, with a
virtual triplet (J=1.9 Hz) for the two vinyl protons. At high field, a
pentet (J=2.95 Hz) was observed for H(3a) which arises from vicinal
coupling to bridgehead hydrogens H(3)-H(7a) and long-range "W" coupling
to endo hydrogens H(7) and H(8).
13
The C NMR spectrum for isomer 39_ was much more complex, with
13 resonances. The question of structure assignment between isomer 39.
and 38^ was resolved by taking advantage of the resulting symmetry of 38
after catalytic reduction of the double bond. Upon removal of the vinyl
carbons in .39, there still remained 13 resonances with two new carbon
signals. Analysis of the selective decoupled high field 300 MHz ^H NMR

17
spectrum was consistent with the structural assignment for _39 (see
Appendix 2).
The mixture of isomers 26. + _38 could not be resolved easily, but on
chromatography with AgNO^ impregnated silica gel, it was possible to
13
achieve a 40:60 enhancement (26_:3£, respectively). A C NMR spectrum
for this mixture revealed 21 resonances, 8 of which were identified as
belonging to _26_, with 13 signals remaining. At this point, the identity
of 38 was still in question. Due to its asymmetry, isomer 40 was also
consistent with this spectrum. To distinguish between these two possibil-
13
ities, the mixture of 26. + _38 was catalytically reduced. The C NMR
spectrum of the resulting mixture exhibited only 16 signals, 8 of which
were again assignable to 26-H^. Therefore, the structure of 38 was
confirmed by its unusual symmetry after reduction.
The remaining postulated isomer 40 was not observed and from
mechanistic considerations is the least likely to be formed. A peak of
similar retention time as the other isomers was observed only in very low
amounts in the GC (<0.6%) and could not be isolated.
Mass Spectra
Examination of the 70 eV GC-MS obtained of the mixture of isomers is
particularly interesting (Figure 2.2). There is a striking similarity of
the spectrum for _37_ compared v/ith _36_. Apparently, isomer 37. fragments
initially (M+ - MeOH = 156) and enters the fulvalene (M+ 156)
manifold. Both compounds exhibit a large 128 peak corresponding to loss
of ethylene to produce a stable fulvalene ion. For the remaining
isomers (26, 38 and 39), the parent ion (m/z 188) is observed as the base
peak in all cases. A very characteristic fragment ion (m/z 123) arises

18
due to a retro-Diels-Alder process (loss of C^H^-) and corresponds to the
intermediate oxonium ion produced in the reaction mechanism for 26. and 3£
(see Scheme 2.5).
Mechanism
The reaction mechanism apparently involves intermediate carbocation
species which can rearrange via various pathways leading to isomers 26,
37-40 as illustrated in Scheme 2.5. Presumably, when the Lewis acid
complexes with ketal _30, it promotes the loss of a methoxide moiety to
generate oxonium ion 29.. The silyl alkylating agent (28) may then
I
OMe OMe
26 39 38 40
Scheme 2.5

19
approach ion 29. from either face (a_: syn to the double bond or _b: anti to
the double bond). Approach from the "wrong side" (_b) produces isomer 37_
after loss of the silyl group and rearrangement. Approach over the
double bond (ji) should be favored sterically to generate intermediate
ion 41, which can suffer either of two fates described by Path I or
Path II. Path I depicts direct loss of the silyl group followed by rapid
[4+2] closure to form 26_. Alternatively, Path II depicts double bond
bridging of the intermediate cation 4T_ to form U2_, which could undergo
Wagner-Meerwien rearrangement. Loss of the silyl group then promotes
closure by any of the four modes indicated to produce 26. and 39-40.
In the presence of BF^*Et20, _26 is formed preferentially, while
AlCl^ favors production of 39. These results may be rationalized by
considering that BF^^Et^O favors early loss of the silyl group (by F
displacement), with subsequent Diels-Alder cyclization producing _26^ as
the major isomer via Path I. On the other hand, AlCl^ is less nucleo¬
philic (toward silyl group displacement) and could favor a longer-lived
carbocation species, which subsequently undergoes further rearrangement
via Path II to produce predominantly isomer 39.
Improved Isolation of 26 from Isomer Mixture
An improved method of purification of 26. was devised which employed
a bromination/debromination procedure. A mixture of the isomers was
treated with B^/C^Cl,-, to brominate the double bond. This gave rise to
a mixture of dibromides which were easily separated by flash chromatog¬
raphy on silica gel. The two major isomers isolated are depicted in
Scheme 2.6 (see Chapter 3 for further discussion of bromination). The
trans-dibromide (26-Brn) was crystalline and facilitated easy clean-up to

20
a high purity (>99% by GC). The debromination was attempted by treatment
25 26
under standard conditions of Zn/EtOH + acetic acid or Zn-Cu couple^
with heating. This gave little success with a large amount of rearranged
dibromide (43) being formed (apparently due to thermal rearrangement).
However, it was noted that utilizing these same conditions, with the reac¬
tion flask immersed in a sonicating cleaning bath, led to a quantitative
debromination in <5 min! It was then determined that bromination of a
clean sample (>97%) of 26. at -60 to -50° C led to pure 26-Br^, without
rearrangement.
This procedure now allows the rapid preparation of 26. in high yield
and purity as illustrated in the overall Scheme 2.6.

Scheme 2.6

CHAPTER THREE
REACTIVITY AND REARRANGEMENTS OF BISESQUINENE
Previous work in our group has investigated the solvolytic behavior
of bisesquinane brosylates to delineate the factors affecting rearrange-
27
ments of these systems. Apparently, there exists a delicate balance
between thermodynamic and bond alignment factors which affect the outcome
of rearrangements in these and other related systems. In the twist-
brendyl system (44), rearrangement into two manifolds is possible due to
28
direct participation by either of two adjacent C-C bonds.
Products derived from 45 predominate by 2.2:1 over those from 46., presum¬
ably due to more favorable C(1)—C(6) bond alignment, even though 46 leads
to a more thermodynamically stable skeleton.
Interconversion of the Wagner-Meerwein related pair, 47 and 48, is
27
believed to involve the O-bridged cation 50. Acetolysis of brosylate
49 produces predominantly acetate 48-OAc with a small amount of acetate
47-OAc, possibly due to leakage from ion _51. to 50.
Acid catalyzed equilibration of acetates 47-OAc and 48-OAc produces the
product ratio 99.5% 48-OAc to 0.5% 47-OAc. This corresponds to a free
energy difference of 3.7 kcal mole ^. Thus, the conclusion was made that
22

23
50 51
thermodynamic considerations favor the participation of bond C(3a)-C(3b)
27
in 48 despite the ideal C(2)—C(8) bond alignment. These findings are
28
contrary to the results of the twistbrendyl system and underscore the
fact that both factors (bond alignment and thermodynamic product stabil¬
ity) must be carefully considered for prediction of Wagner-Meerwein
rearrangements.
Acid Catalyzed Rearrangements in Methoxybisesquinene
Previous results by Grob and co-workers have demonstrated the facile
cleavage on solvolysis of 6-exo-substituted-2-exo-norbornyl toluene-
sulfonates (52) by a concerted fragmentation involving rupture of the
C(l), C(6) bond in cases where the substituent is an ¿-electron donor,
such as CH3S, CH30, HO, or (CH^N.29,30
52
53
54

24
31
These accelerated cleavages have been called "frangomeric effects" and
operate in the 6-norbornyl case to produce exclusively the intermediate
salts 53_ which are immediately hydrolyzed to (3-cyclopentenyl)acetalde-
hyde (54). Another example of this type of cleavage was reported by
32
Gassman and Macmillan for the ketal _55 which, on solvolysis followed by
reduction with lithium aluminum hydride (LAH), produced (3-cyclohexyl)-
methanol (57) in 57% yield.
Previous work on dimethyl ketal _58 showed no similar
instead produced the 2-exo-methoxy-7-norbornone (61)
33
group participation of the syn-methoxy moiety.
fragmentation but
via neighboring
OMe
58
59
50
This difference of reactivity can be explained as a result of "tying
back" the syn-oxygen in ketal 55. to inhibit its participation and
thereby afford the anti-oxygen the opportunity to participate in the
frangomeric cleavage.
In view of the frangomeric effect, the results for the unsubstituted
bisesquinane (47) solvolysis and acid catalyzed rearrangements prompted
us to consider the effect of a methoxy substituent on carbon-3b (e.g.,
methoxybisesquinene, 26). Under acidic conditions (see Scheme 3.1), it

25
Scheme 3.1
was anticipated that the methoxy moiety should facilitate the leakage of
ion _62 to ion 63a and thence to the localized cation 63b. The presence
of ion 63b would be manifested by the formation of ketone 66. Solvent
capture by either ion 62. or ion 63a could produce products 64-X and 65-X
Product 64-X could also arise from direct addition to the double bond in
26 before rearrangement to ion 62.
Addition Reactions of the Double Bond
A series of electrophilic addition reactions to the double bond of
bisesquinene (26) were studied to gain insight into its unusual reactiv¬
ity and tendency toward rearrangement.
One of the first indications of this unusual reactivity was the
observation that the neat methoxybisesquinene (26) on standing several
months in the refrigerator partially decomposed to produce a polymeric
material and the exo-epoxide (67). This epoxidation is presumably due
to facile air oxidation of the alkene.

26
That this material was the exo-epoxide was demonstrated fay the authentic
synthesis of 67_ by treatment of _26_ with 3-chloroperoxybenzoic acid
(MCPBA), which produced the single exo-isomer _67_ (87% yield). The NMR
spectrum contained a very characteristic singlet (6 3.24, 211) for the
endo hydrogens adjacent to the epoxide confirming its expected exo stereo¬
chemistry.
Bromination of the double bond in methoxybisesquinene (26) at room
temperature produced a mixture of isomers 26-Br^ and 43_ (82% and 18%,
respectively).
The rearrangement to dibromide 43 probably proceeds via bromonium ion 68a
and a subsequent Wagner-Meerwein shift to 68b. When the alkene _26 is bro-
minated at -78 to -60°C, only the crystalline trans-dibromide 26-Br^ is
produced with no evidence for the rearrangement product 43. The structure
of 26—Br0 was confirmed by x-ray crystallography and is discussed in Chap¬
ter Four. Tne NMR spectrum for 26-8^ was distinctly different from

27
that of the rearranged dibromide 43, with elements of its pseudo-symmetry
apparent. The signal for H(3a) was still quite clearly a pentet
(J=2.7 Hz) in 26-Br^, while in 43 it was observed as a broad multiplet.
The most characteristic signals came from the protons alpha to Br at
6 4.53 (dd, J=2.7, 5.2 Hz) and 6 4.19 (d, 2.7 Hz), corresponding to the
exo and endo hydrogens, respectively, in 26-Br,-,. The corresponding
protons in 43 appeared at ó 4.85 (broad t, J=1.2 Hz) and 6 4.08
(t, J=1.46 Hz).
That the double bond of methoxybisesquinene (26) is particularly
susceptible to acid was first realized during the attempted de-methyla-
tion with trimethylsilyl iodide (TMS-I). This reaction is thought to
proceed by complexation of the ether oxygen with the silyl moiety fol-
lowed by S,,2 displacement of the methyl group by iodide.
R-O-Me + TMS-I > R-0—Me I > R-O-TMS » R-OH
1
TMS Mel
Subsequent hydrolysis of the silyl ether produces the desired alcohol.
However, treatment of alkene 26_ with TMS-I did not produce the expected
alcohol. Instead, a complex mixture resulted which, upon GC-MS analysis,
indicated that addition of HI to the double bond had occurred. The major
product was isolated by prep GC and tentatively identified as exo-iodide
64-1 based on ^H NMR and MS fragmentation patterns.

28
The formation of HI could result from adventitious water present in the
reaction or upon quenching of excess TMS-I on work-up. Removal of the
double bond by reduction followed by treatment with TMS-I led to clean
production of the saturated alcohol (see Chapter Four), thus demonstrat¬
ing the sensitivity of the alkene to acid addition.
Preparation of Acid Rearrangement Products
To study the acid catalyzed rearrangements of _26_, we needed
authentic samples of the possible alcohols, acetates and ketone. The
epoxide 67_ was opened smoothly with diisobutylaluminum hydride (DIBAL-H)
to produce a clean sample of exo-alcohol 64-OH (78.5% yield). The Hi NMR
spectrum of exo-alcohol 64-OH exhibited a quite characteristic pattern of
doublet of doublets (6 3.94, J=2.4, 7.1 Hz) for the endo-hydrogen alpha
to the hydroxyl moiety. The carbon spectrum contained only 12 visible
peaks, but one was slightly more intense, suggesting overlap. The INEPT
pulse sequence confirmed the presence of 3 methylene peaks, two of which
were almost superimposed, indicating the molecule's more symmetrical
appearance at sites removed from the added functionality.
OMe
It was anticipated that the rearranged alcohol 65-01? could be
obtained by the reaction sequence as outlined in Scheme 3.2. This
approach depends upon a previously described rearrangement of epoxide 69

29
to alcohol 70, apparently via carbene insertion into the bridge C-H
69
70
Treatment of alcohol 71 with sodium hydride and methyl iodide cleanly
produced the methyl ether 72. (98% yield). Epoxidation was smoothly
accomplished with 3-chloroperoxybenzoic acid (MCPBA) to yield epoxide 73
(95% yield). Attempted rearrangement of epoxide 73 with lithium diethyl¬
amide in refluxing diethyl ether (Et20) gave only starting material on
work-up. However, refluxing in THF with lithium diethylamide produced
the desired alcohol 65-0H (53% yield). A point of confusion arose
initially in that both epoxide 73. and alcohol 65-0H had identical
retention times on the GC capillary column being utilized; however, the
transformation of 73 to 65-0H was readily distinguished spectroscopically
due to its loss of symmetry. The ^H NMR spectrum for 55-OH contained a
diagnostic doublet 6 A.3 (J=2.4 Hz) for the hydrogen alpha to the -OH,
13
which is quite characteristic for this twisted ring system. The C NMR
spectrum clearly indicated rearrangement of the symmetrical epoxide _62_
(8 signals) to the unsymmetrical alcohol 55-QH (12 signals, one peak
overlapped).
Ketone _66 was also obtained as previously described from alcohol _71_
37
by treatment with pyridinium dichromate (Scheme 3.2).

30
Scheme 3.2
Alcohols 64-OH and 65-OH were cleanly converted to their correspond¬
ing acetates by treatment with acetic anhydride in the presence of a
OO 1 1 o
catalytic amount of dimethylaminopyridine (DMAP). The iH and JC NMR
spectra were not significantly changed except for the observation of the
acetate residue.
Ac20
DMAi^
Results of Acid Addition to the
Double Bond of Methoxybisesquinene (26)
With the probable products of acid addition to methoxybisesquinene
in hand, it was now a simple matter to identify the rearrangement prod¬
ucts. The results of the treatment of methoxybisesquinene (_26^ with
various acids are summarized in Table 3.1. In no case was the formation
of ketone 66 observed.

31
Table 3.1. Acid Catalyzed Rearrangement of Methoxybisesquinene (26)
26
Add
â–º
R
Conditions
0
Product Ratio
0
II
cf3c- tfa/cdci3 90 10
RT, 12 h
0
II
CH3C- HOAc/TsoH 60 40
60°C
30 days
H- H2S04/H20/THF 86 14
38% :21%:41%b
(1 : 1 : 2) vol
RT, 6 h
H- H„S0,/Ho0/THF 36 64
2 4 2
60% :20%:20%
RT, 4 h
H- 40% H„S0./H„0
2 4 2
a) 60°C, 2 h 24 76
b) 60°C, 12 h <1 99
a Determined by capillary GC; no other significant products were
detected
b wt/wt%

32
Trifluoroacetic acid (TFA) adds rapidly at room temperature to
methoxybisesquinene (26) in CDCl^ solution, producing a 90:10 ratio of
64-TFA and 65-TFA, respectively. The 64-TFA isomer was isolated and
1 13
fully characterized. Its H and C NMR spectra were quite similar to
64-0Ac. The mixture of TFA-isomers was treated with DIBAL-H and con¬
verted cleanly to a mixture of alcohols 64-0H and 65-0H, for confirmation
of their structures by GC retention times.
Treatment of methoxybisesquinene (26) with glacial acetic acid and
catalytic tosylic acid, although much more sluggish, gave similar
results. The mixture was maintained at 60°C for 30 days and resulted in
the partial equilibration of acetates 64-0Ac and 65-OAc (60:40, respec¬
tively), with ca. 18% unreacted methoxybisesquinene (26) remaining. To
assess the equilibration, acetate 64-0Ac was heated in glacial acetic
acid, 1% acetic anhydride, and catalytic tosylic acid at 75°C. After
1 week, GC analysis indicated a relative ratio of 45:55, 64-0Ac to
65-0Ac, respectively. Allowing the equilibration to continue for an
additional week produced a relative ratio of 16:84. The equilibration is
cleárly quite slow under these conditions. Noteworthy is the fact that
no additional products appeared.
The results of sulfuric acid catalysis indicate a significant
increase in the rearrangement of 64-OH to 65-0H with increasing acid
strength and temperature. Tetrahydrofuran (THF) was used as a cosolvent
to maintain solubility, however, analysis was complicated by the

33
formation of THF decomposition products. This problem was circumvented
by use of I^SO^/^O solutions without THF, and although this resulted in
a heterogeneous mixture, clean conversion of methoxybisesqinene 26. to
alcohols 64-OH and 65-OH was observed.
To determine the stability of ketone 66^ under these conditions, the
ketone was treated with acid as above (40% ^30^^20, 60°C) for 2.5 hr.
Upon GC analysis, there was no trace of ketone _56, but a new peak was
observed at longer retention time (which had not been observed in any of
the previous acid rearrangements of methoxybisesquinene). The NMR
spectrum of the crude reaction mixture exhibited somewhat broadened peaks
suggesting a mixture of polymeric material. After prep TLC, a relatively
pure material was obtained, and its ^H NMR spectrum was remarkably simi¬
lar to that of 65-OH, exhibiting a characteristic doublet (5 4.4 ppm,
J=2 Hz)and a parent ion of 192 m/z in the GC-MS. This material is tenta¬
tively identified as the diol _74 and could originate as shown:
66
74
Confirmation of this structure was attempted by treatment of 65-OH
with TMS-I in C^D^ to effect de-methylation and hopefully produce diol
74. As the reaction was monitored in the ^H NMR, broadening of the
proton alpha to the -OH occurred, and a new methoxy signal began to
appear soon after the addition of TMS-I. At longer times, both methoxy
peaks diminished as a peak for methyl iodide developed. After standing
overnight, the signals for -OMe virtually disappeared. Following work-up,
gas chromatographic analysis confirmed the absence of starting material

34
(65—OH) and showed two new major peaks at 5.23 min (25.8%) and 7.88 min
(68.2%) and two minor components at 7.63 min (2.82%) and 8.05 min (3.25%).
The peak at 5.23 min corresponded to the retention time for ketone 66.
but the later peaks were at longer times than diol _74_ (6.68 min). The
NMR spectrum showed a broadened doublet (6 4.8, J=2 Hz) which was quite
similar to the rearranged ring system but no evidence of a vinyl peak at
5 6.0 for ketone 66. Analysis of the mixture by GC-MS confirmed the
presence of ketone 66^ (M+ 174, 19%); however, the later peaks were
extremely broad due to decomposition on the column and, except for m/z
175 (10%), showed only mass fragments corresponding to ketone 66.
Analysis of the mixture by direct vaporization on the solids probe
allowed detection of a small molecular ion at m/z 302 (0.33%), a now
substantially larger peak at m/z 175 (100%, M+-I), and peaks for HI+
(128, 55%) and I+ (127, 33%), which indicate the formula C^H^rOI.
Therefore, the major component is tentatively identified as iodo-alcohol
78 which may be formed as shown in Scheme 3.3.
The NMR results may be explained by formation of an initial silane
complex (75) followed by rearrangement to ion 76 or 63a. Collapse of the
ion pair (76 or 63a) would produce 64-1 and 65-1, which would account for
the broadened alpha proton and shifted -OMe signals. A second equivalent
of TMS-I then complexes with the -OMe and after work-up produces iodo-
alcohols 77_ and 78^. Since there was no observation of the ketone 66
vinyl during the reaction, we suggest the capillary GC results (peak at
5.23 rain) are due to thermal rearrangement in the injector of 78_ with
loss of HI. This is consistent with the GC-MS observations which
utilized a packed glass column (more reactive surface for decomposition
compared to fused silica).

35
Scheme 3.3

36
Conclusions
Apparently the addition of the methoxy moiety to the C(3b) position
of bisesquinene has little effect as far as the predicted frangomeric
cleavage of bond C(3b)-C(3a) to produce ketone 66. These results imply
that ion 63a does not contribute significantly to the rearrangement of
the bisesquinane skeleton since leakage to 63b and thence to ketone would
be expected. A better representation of ion 63a may be the degenerate
rapidly equilibrating ions (79a and 79b).
OMe
79a
79b
It is difficult to rationalize why we did not observe any ketone 66_ or
subsequent ketone-derived products, since the energy of bond C(3b)-C(3a)
cleavage should be regained by formation of the carbonyl. In addition,
39
strain energy calculations for the related hydrocarbon ring systems
show that the skeleton of 6(3 is ca. 4 kcal/rnole more stable than that of
65. However, additional strain is contributed by the double bond and
carbonyl and may significantly raise the strain energy of 66 to a level
comparable or even higher than that of 65-OH. As a consequence, there
would be little driving force for frangomeric cleavage to occur. Some
support for this argument is the rearrangement of ketone 6(3 under acid
conditions to the 65-X framework.

CHAPTER FOUR
STRAIN AND STRUCTURAL EFFECTS
IN THE BISESQUINANE SYSTEM
Relief of skeletal strain is frequently cited as a contributing
40
factor in rearrangements of polycyclic skeletons to more stable ones.
When predicting and interpreting these skeletal rearrangements, it has
been helpful to use computer calculations of strain energies to compare
41 42
molecular stabilities of possible products. ’ In this fashion, the
chemist can gain insight into the complexities of a reaction, and more
accurately determine the probable fate of a rearrangement which could
follow more than one course. A study of the structure and inherent ring
strain in the parent bisesquinane (4_) and its effects on reactivity and
rearrangements is presented here. The goal of this study is to discrimi¬
nate between various C-C bonds in order to partition the overall ring
strain and assign the "most strained" portions of the molecule.
Strain Energy
MM2 Calculations
Molecular mechanics calculations of strain energy utilizing
43
Allinger's MM2 program were carried out on the parent bisesquinane
(_4) and compared with various derivations obtained by 1-bond cleavages
(see Figure 4.1). The molecular mechanics method calculates a geometry
for the molecule which minimizes its total energy. The amount of strain
37

o
82
29.28
Figure 4.1. A) MM2 calculations of strain energy
165.9
LO
CO
a Engler force field39
b Allinger force field (MM1)39
B) Representative strain energies

39
present is reflected by the extent to which the molecule's structural
parameters (bond angles and lengths) deviate from their ideal values in
order to reduce the molecule's total energy. As can be seen from
Table 4.1, the total steric energy (E) results from the summation of
several contributing energies: bond compression (or stretching), bond
bending (angle distortion), stretch-bend, van der Waals (non-bonded inter¬
actions between atoms or groups), and torsional (function of dihedral
angle). Inspection of these energy factors for compounds _4, 80-82 is
instructive in determining the major sources of high steric energy. In
all cases, the torsional interactions contribute greatly to the observed
steric energy. These bridged polycyclic systems, by their nature, force
sterically demanding eclipsing interactions which give rise to the ob¬
served large torsional energies (20-26 kcal/mole). Another major contri¬
bution to steric energy comes from the bending, which decreases substanti¬
ally (32-6 kcal/mole), as angle strain is relieved. Most of the other
energy factors are relatively insignificant, except for the van der Waals
1,4 interactions (4-9 kcal/mole). Interestingly, in the bisesquinane
skeleton (4_), these interactions are the lowest of the four compounds
compared.
The bond enthalpy (BE) and strainless bond enthalpy (SBE) can be
calculated from standard values for the total number and types of bonds
in the molecule. The partition function contribution (PFC) is the sum of
population (POP), torsional (TOR), and translation/rotation (T/R) contri¬
butions and is constant for all four structures due to their rigidity.
Utilizing these values and the steric energy (E), the heat of formation
(HFO) may be obtained from the following equation:
HFO
E + BE + PFC

40
Table 4.1. MM2 Energy Calculation Results (kcal/mole)
Compression
4
1.5970
80
2.144
81
1.409
82
0.970
Bending
32.332
22.211
15.598
6.074
Stretch-Bend
-1.375
-0.899
-0.546
-0.187
van der Waals <
fl ,4
4.345
7.481
8.917
6.479
Other
-2.043
0.597
-2.298
-2.356
Torsional
24.238
19.677
20.972
26.289
Total Steric Energy (E)
59.093
52.211
44.051
37.269
Bond Enthalpy (BE)
-50.72
-57.28
-57.28
-57.28
Strainless Bond Enthalpy (SBE)
-42.70
-49.29
-49.29
-49.29
Population (POP)
0.00
0.00
0.00
0.00
Torsional (TOR)
0.00
0.00
0.00
0.00
Translation/Rotation (T/R)
2.40
2.40
2.40
2.40
Partition Function
Contribution (PFC)
2.40
2.40
2.40
2.40
Heat of Formation
(HF0) = E + BE + PFC
10.77
-3.67
-10.83
-17.61
Strainless Heat of Formation
(HFS) = SBE + T/R
-40.30
-46.89
-46.89
-46.89
Inherent Strain
(SI) = E + (BE-SBE)
51.07
43.22
36.06
29.28
Strain Energy
(S) = POP + TOR + SI
51.07
43.22
36.06
29.28

41
The strainless heat of formation (HFS) results from the translation/rota¬
tion addition to the strainless bond enthalpy (SEE):
HFS = SBE + T/R
The inherent strain (SI) is calculated by adding the steric energy (E)
to the difference between the bond enthalpy (BE) and strainless bond
enthalpy (SBE):
SI = E + (BE - SBE)
Finally, the strain energy (S) is obtained by correcting the inherent
strain (SI) for any torsional (TOR) and population (POP) contributions:
S = SI + TOR + POP
These results predict the greatest relief of strain (ca. 22 kcal/mole)
when cleaving the central bond _c which correlates well with previous
g
experimental observations. Thus, in the case where this bond is substi¬
tuted with diester groups (10), facile cleavage occurs to produce the
tetraquinacene 13.
E
10 13
Homoketonization
The calculated strain energies of SO and 81_ reveal a 7 kcal/mole
preference for breaking bond _b over bond a_ in bisesquinane (4). To

42
devise an experimental test for the relative bond strengths of a_ and _b in
the bisesquinane system (i.e., which is more highly strained?), we consid-
44
ered a homoketonization type rearrangement. Generally, this can be
considered as the reverse homo-enolization process depicted below for
camphenilone (83)
83
Homo-enolization
Homoketonization
There are numerous examples of base-induced homoketonization, from
which some general factors relating to control of the regiochemistry of
the cleavage can be obtained. Relief of strain, product stability, and
the stability of the incipient carbanion are the major considerations for
determining regiochemistry. For example, preferential cleavage of bond a.
in 85 results from the delocalization of the incipient carbanion (86) and
46
produces aldehyde 88_ exclusively.
Relief of strain and product stability dictate bond cleavage in 89 which
47
leads to the formation of noradamantone (90).

43
39 90
The bisnoradaraantyl alcohol (91) horaoketonizes in t-BuOK/t-BuOD (70°C) to
yield exclusively 92_, resulting from cleavage of bond a_ with retention
of configuration.^
In the case of the hydroxybisesquinane skeleton (93), these concepts
were utilized to probe the relative bond strain of a_ and _b as illustrated
in Scheme 4.1. If homoketonization occurs, a choice of which bond(s) to
break must be made. Cleavage of bond a_ would lead to "homo-enolate" _94
while cleavage of bond _b would produce "homo-enolate" 95.. Inspection of
molecular models indicates that in 94, the carbanion is rigidly held in
close proximity to the newly formed carbonyl (unlike the intermediate
95
Scheme 4.1

44
carbanion in the transformation of 9l_ to 92). Hence, we might expect
rapid equilibration to reform bond a_. However, this is not the case in
the formation of £5 since, due to the greater flexibility of the newly
opened cyclohexyl ring, the carbanion is removed from the vicinity of the
carbonyl. Thus after equilibration, we would expect to produce the more
thermodynamically stable ketone via "homo-enolate" 95.
Armed with these predictions, we attempted to confirm them experimen¬
tally (Scheme 4.2). In this regard, methoxybisesquinene (26) was con¬
verted by reduction to methoxybisesquinane (26-H^). This v/as cleanly
de-methylated to the crystalline bisesquinol (96) by treatment with
trimethylsilyliodide (TMS-I). The bisesquinol (96) was subjected to
homoketonization conditions similar to those utilized for 9J_ (t-butoxide/
t-butanol, 90°C, 20.75 h), and GC analysis indicated only starting
material present. Under more vigorous conditions (200°C, 22 h) GC analy¬
sis indicated a mixture of starting material (20%) and a single major new
component (72%). The mixture was fractionated by prep TLC to afford a
-1 13
ketone, as evidenced by IR (1740 cm ). The C NMS spectrum showed the
presence of 12 peaks, thereby excluding ketone _97 (by symmetry only
1 3
7 peaks are expected). The INEPT C NMR spectrum (Figure 4.2) clearly
shows the presence of 5 methylene peaks and 6 methine peaks, consistent
with the structure of ketone 98.
In summary, we have shown that exclusive cleavage of bond _b occurs
to produce the more stable ketone _98_ in preference to ketone 97.

45
Homoketonizatlon
Scheme 4.2

Figure 4.2.
INEPT 13C NMR
spectrum of ketone 98.

47
Bisesquinane Structure: Calculated and X-Ray
Bond Lengths
From the MM2 calculations, we can obtain structural information
regarding bond lengths and bond angles. One might suspect that a more
strained bond, as a consequence, would be longer than normal. Close
inspection of the calculated bond lengths of bisesquinane (4^
(Figure 4.3) reveals that bonds a_ and c_ are the longest bonds. That
this is indeed significant becomes more obvious when comparison is made
with compounds 80 and 81_. There is a clear trend indicating that as the
strain is relieved in the molecule, the bond lengths tend toward the
normal C-C bond distance of 1.54 X.
To substantiate the theoretical prediction of longer bond lengths
for bonds a_ and c_, an x-ray crystal structure was obtained for the
dibromomethoxybisesquinane derivative (26-Br^). An ORTEP drawing of
the crystal structure for 26-Br9 is presented in Figure 4.4 and a summary
of the bond lengths in Tables 4.2 and 4.3.
Figure 4.4. Stereoscopic view of the molecular structure of 26-6^

48
Figure 4.3.
MM2 calculated bond lengths.

49
O _
Table 4.2. Bond Lengths [A] with Estimated Standard Deviations in
Parentheses for Dibromide 26-Br^ Involving Non-H Atoms
Br(1)-C(2)
1.968(8)
Br(2)-C(3)
1.987(8)
C (2 ) —C (1)
1.500(11)
C(3)-C(4)
1.490(12)
C(1)—C(12)
1.530(12)
C(4)-C(5)
1.549(11)
C(l)-C(ll)
1.556(10)
C(4)-C(ll)
1.561(11)
C(9)—C(12)
1.539(12)
C(6)-C(5)
1.515(12)
C (9) —C (8 )
1.523(13)
C(6)-C(7)
1.523(13)
C(9)—C(10)
1.516(11)
C(6)-C(10)
1.553(11)
C (2) —C (3 )
1.515(12)
C(7)-C(8)
1.538(13)
C(5)—C(12)
1.612(11)
C(10)-C(ll)
1.588(11)
0(l)-c(10)
1.423(9)
0(1)-C(13)
1.398(10)

50
Table 4.3.
o
Bond Lengths [A]
for Dibromide 26-6^ Involving
H Atoms
H( 2)—C(2)
1.16
H(3)—C(3)
1.06
H (1) —C (1)
0.98
H(4)-C(4)
0.94
H(12)—C(12)
1.04
H(5)-C(5)
1.14
H(9)-C(9)
1.11
H(6)-C(6)
1.16
H (81) —C ( 8)
1.00
H(71)-C(7)
1.01
H (8 2) —C (8)
1.15
H (7 2 ) —C (7)
1.01
H(11)—C(11)
1.00
H(M1)—C(13)
0.95
H(M2)-C(13)
0.74
H(M3)-C(13)
0.95

51
The bond lengths are grouped according to similar bond types for facility
of comparison. It is immediately obvious that the conclusions based upon
M2 calculated bond lengths are reflected in the long bond lengths of
a [C(10)—C(11) = 1.488 A] and c_ [C(5)—C(12) = 1.612 A] in the crystal
structure of 26-Br^. It appears that the tendency of the bisesquinane
skeleton is to relieve large strain contributions by stretching these two
bonds.
Bond Angles
Marked distortion of bridgehead angles from tetrahedral has been
49
cited as a major source of skeletal strain. Calculation by MM2 of bond
angles in 4_, 80 and 8_1 (Figure 4.5) reveals cases of substantial compres¬
sion and accounts for a large portion of the strain energy of these mole¬
cules. Comparison of bond angles in norbornane^’ with those calcu¬
lated for bisesquinane (_4) is very informative. As expected, the
central bridge angle C(1)—C(11)—C(4) at 93.0° is approximately equal to
the norbornane bridge angle of 93.1°. Somewhat surprising is the angle
C(5)-C(4)-C(ll) which is compressed even more to 91.4°! This compares
with the similar norbornane angle at 101°. Careful examination of the
model of bisesquinane reveals that this unusual bond angle is a conse¬
quence of the molecular framework. Viewed from a different perspective
(Figure 4.6), this "bridgehead" carbon (in the sense of norbornane)
becomes a "bridge" carbon; consequently, the 91.4° bond angle appears to
be somewhat more normal.

52
Figure 4.5
MM2 calculated bond angles=and Z values
(see text).

53
Table 4.4. Bond Angles [°] with Estimated Standard Deviations in Paren¬
theses for Dibromide 26-Br„
Br (1) —C ( 2) —C ( 3)
110.6(6)
Br (1) —C ( 2) —C (1)
113.7(6)
C (1) —C (2 ) —C (3)
104.2(7)
C(2)—C(1)—C(11)
104.7(6)
C(2)—C(1)—C(12)
115.8(7)
C(11)—C(1)—C(12)
93.8(6)
C(1)—C(12)—C(9)
98.7(6)
C(1)—C(12)—C(5)
102.4(6)
C(5)—C(12)—C(9)
101.4(6)
C (12) —C (9) —C (8)
114.6(7)
C(12)—C(9)—C(10)
93.2(6)
C (10) —C (9) —C (8)
105.9(7)
C (9) —C (8) —C (7)
103.8(7)
C(l)-C(ll)-C(10)
103.0(6)
C(11)—C(10)—C(9)
104.9(6)
C(1)—C(11)—C(4)
92.6(6)
C(9)—C(10)—0(1)
113.1(6)
C(ll)-C(10)-0(1)
117.2(6)
Br(2)-C(3)-C(2)
110.3(6)
Br(2)-C(3)-C(4)
112.2(6)
C(4)-C(3)-C(2)
104.1(7)
C(3)-C(4)-C(ll)
107.5(6)
C(3)-C(4)-C(5)
112.0(7)
C(ll)-C(4)-C(5)
93.2(6)
C(4)-C(5)-C(6)
99.7(6)
C(4)-C(5)-C(12)
101.6(6)
C(12)-C(5)-C(6)
103.1(6)
C(5)-C(6)-C(7)
113.7(7)
C(5)-C(6)-C(10)
92.4(6)
C(10)-C(6)-C(7)
105.9(7)
C(6)-C(7)-C(8)
103.6(7)
C(4)-C(ll)-C(10)
103.1(6)
C(ll)-C(10)-C(6)
104.9(6)
C(9)-C(10)-C(6)
94.8(6)
C(6)-C(10)-0(l)
119.0(6)
C(10)-0(l)-C(13)
113.8(6)

54
Table 4.5. Bond Angles [°] for Dibromide 26-Br Involving H Atoms
H(2)-C(2)-Br(l)
109
H(3)-C(3)-Br(2)
109
H (2) —C (2) —C ( 3)
107
H(3)-C(3)-C(2)
118
H ( 2) —C (2 ) —C (1)
112
H(3)-C(3)-C(4)
104
H (1) —C (1) —C (2)
115
H (4) —C (4 ) —C (3)
117
H(1)—C(1)—C(11)
112
H (4)—C(4)—C(11)
107
H(1)—C(1)—C(12)
114
H (4) —C (4) —C (5)
117
H(12)—C(12)—C(1)
121
H (5) —C (5) —C (4)
120
H(12)—C(12)—C(5)
114
H(5)—C(5)—C(12)
111
H(12)—C(12)—C(9)
116
H (5) —C (5) —C (6)
119
H(9)—C(9)—C(12)
110
H (6) —C (6) —C (5)
112
H(9)—C(9)—C(10)
110
H(6) —C(6)—C(10)
112
H (9) —C (9) —C (8)
119
H (6) —C (6)—C (7)
118
H(81)-C(8)-C(9)
122
H (71) —C (7) —C (6)
109
H (81) —C (8) —C (7)
102
K (71) —C (7) —C (8)
112
H(81)-C(8)-H(82)
98
H(71)—C(7)—H(72)
109
H (8 2) —C (8) —C C 9)
115
H (7 2 ) —C (7) —C (6 )
109
H (8 2) —C (8) —C (7)
116
H (7 2 ) —C (7) —C (8)
114
H(11)—C(11)—C(1)
118
H (11)—C(11)—C(4)
121
H(11)—C(11)—C(10)
116
H(M1)—C(13)—0(1)
108
H(M2)—C(13)—0(1)
113
H(M3)-C(13)-0(1)
106
H(M1)-C(13)-H(M2)
79
H(M1)-C(13)-H(M3)
116
H(M2)-C(13)-C(M3)
131

55
Figure 4.6. Perspective drawings of bisesquinane (4J).
One method of gauging bridgehead angle distortion is to compare the
sum of the three internal skeletal angles around the central bridgehead
carbon (Z value, Figure 4.5). The Z value for norbornane is 311 which,
when compared to the normal tetrahedral arrangement (£ = 328.5° from
109.5 x 3) indicates significant angle distortion. Inspection of
Figure 4.5 reveals a trend in the Z values for compounds 4_, 80 and 81.
Apparently in bisesquinane (4_), C(11) and C(5) possess significantly
more angle strain than C(4). Cleavage of bond a or _b (GO or ^8]J results
in a substantial increase of the £ value for C(5), thus indicating a
decrease in angle distortion (i.e., the values become much more tetrahe¬
dral-like as bonding restrictions are relieved).
13
C-ii Spin-Spin Coupling and Angle Strain
13
It is well known that the C nuclear spin-spin coupling constant
appears to be a linear function of the amount of s-character in the
carbon-hydrogen orbital.A linear relationship has been demonstrated
between the nuclear spin-spin coupling constant and C-C-C bond
52
angles in simple cyclic hydrocarbons. This correlation has been
attributed to a change in hybridization to increase the s-character in
external bonds as internal bond angles are decreased. It has been
suggested that the decreased internal skeletal bond angles of norbornyl

56
derivatives require an increase in the p-character of the bridgehead car-
49
bon bonds. As a result, there is an increase in the s-character of the
53
bridgehead C-H bonds. Although estimates of % s-character have been
made using the simple relationship % s = Jj-,_^/500, quantitative extrapola¬
tion of % s-character in strained systems directly from ^ is not now
considered justified.'^ However, one can still make qualitative com¬
parisons of angle strain by inspection of coupling constants.
Figure 4.7 summarizes the coupling constants for methoxybisesquinene (26)
along with values for other related bicyclic systems. Based on our previ¬
ous analysis of angle distortion in bisesquinane (£ values), we predicted
enhanced s-character (and consequently larger coupling contants) for
C(ll) and C(5); however, there is no apparent correlation. Noteworthy is
the unusually high value coupling constant for the central carbon C(5)
(J=150.8 Hz) when compared to C(l) (J=144.6 Hz). The effect of decreas¬
ing skeletal bond angles can be seen clearly by comparing bicyclo[2.2.2]-
octene (J=134 Hz) with norbornene (J=145 Hz). Considering norbornane,
norbornene and norbornadiene, there is an obvious trend of increasing
in the bridgehead carbons as the ring strain is increased (ca. 3 Hz/
double bond). The bridgehead [C(4) and C(6)] coupling constants for
methoxybisesquinene correlate reasonably well to what one might predict
based on a simple "fusion" of norbornadiene and norbornane.
Interplanar Angles
An unusual consequence of the molecular framework in bisesquinane
(4_) is the "tying back" of the two bridging methylenes by bond a. This
structural effect may be seen clearly in the crystal structure of 26-Bro
as viewed down the C(5)-C(12) bond (Figure 4.8).

57
OMC
135
136 134
132-2
131-134
55,56
, 7 13C-H Coupling constants.
Figure 4./• ^

58
Figure 4.8. Crystal structure of 26-Br,-, as viewed down the C(5)—C(12) bond.
Interplanar angles were calculated by a least-squares type analysis for
26-Br,, from x-ray crystal data, bisesquinane (4.) and exo-exo-sesquinor-
49
bornane (80) from MM2 structures, and norbornane ' (Figure 4.9). The
results show a substantial opening of the exo face of bisesquinane
(136.7°), compared to norbornane (123.5°). Interestingly, the exo face
of sesquinorbornane (80) is compressed (117.4°) due to van der Waals
repülsions between the internal bridge hydrogens.
Diels-Alder Reactivity of Bisesquinene:
Adduct Stereochemistry
It is well established that norbornene is a reasonably reactive
dienophile in Diels-Alder reactions with activated dienes and generally
gives exo adducts.^ Because of its structural similarity with norbor¬
nene, we have investigated the reactivity of methoxybisesquinene (26^) as
a novel dienophile. It was anticipated that the greater accessibility of
the exo face of methoxybisesquinene may affect the stereochemistry of the
resulting adducts.

OMe
Figure 4.9. Interplanar angles.

60
The determination of Diels-Alder adduct stereochemistry has been the
subject of many investigations utilizing various chemical and physical
methods including Cope rearrangements,intramolecular cyclization,"^
NMR proton-proton coupling,^ solvent induced shift method,^ phenyl
62 63
multiplicity method, and x-ray crystallography. All of these methods
suffer from limitations v/hich have hampered research in this area.
A fairly recent addition to the list of physical methods utilizes
13
coupled C NMR to probe adduct stereochemistry. It has been shown that
3
^C-H couPlin§ :*-s dependent upon the torsion angle

64-
nuclei in a Xarplus-type relationship. The method is particularly
useful for bridged carbonyl adducts of tetraphenylcyclopentadiene (tetra-
cyclone) and has been called the "carbonyl multiplicity technique."0^
The adduct 99. derived from tetracyclone and diethyl fumarate exhibits a
doublet (J = 7.1 Hz) for the carbonyl resonance in the coupled C NMR.
The splitting results from long-range coupling only between the carbonyl
and the endo proton (H-2, j) = 160-170°) since the exo proton (II—3) is
improperly aligned ((¡) = 90°). Consequently, it is now a simple to distin¬
guish between exo and endo adducts by examination of the long-range car¬
bonyl coupling patterns (eg., 100 = triplet, 101 = singlet).
99
100
101

61
Preparation of Adducts
Diels-Alder adducts of methoxybisesquinene (26) were prepared from
the dienes tetraclorodimethoxycyclopentadiene (102) and tetracyclone
(104). A benzene solution of methoxybisesquinene (26) and tetrachloro-
dimethoxycyclopentadiene (102) was heated at 80°C for 10-12 hr to cleanly
produce the single crystalline adduct 103 (69% yield).
(endo, exo) (exo, exo)
Tetracyclone (tetracyclone, 104) is a much less reactive diene than
ketal 102 and requires more vigorous conditions for reaction with 26.
Tetracyclone has a characteristic deep purple color which disappears upon
cycloaddition and thus provides a convenient indicator of the reaction
progress. Gentle heating to melt a 1:1 mixture of methoxybisesquinene
(26) and tetracyclone (104) produces the crystalline adduct 105 and a
substantial amount of the decarbonylated diene 106 (25% and 68% yield,
respectively). The mixture was cleanly separated by prep TLC (benzene)
to remove the unreacted purple tetracyclone (104) and the decarbonylated
diene (106) which showed a characteristic blue fluorescence under UV
light. Adduct 103 melted with decomposition (mp 215° dec) to liberate CO
and also turned pink indicating some retro-cycloaddition back to tetracy¬
clone. This behavior is quite normal for tetracyclone adducts which have
62
been shown to readily decarbonylate.

62
Stereochemistry
The exo stereochemistry (with respect to the bisesquinane ring
system) of the adduct 103 was confirmed in the NMR spectrum by the
lack of vicinal coupling between the endo hydrogens H-1,2 (6 2.64, s) and
bridgehead hydrogens H-3,7a (6 2.32, d, J=2.7 Hz; coupled to H-3a). The
relative stereochemistry of the dimethoxy bridge is not readily discern¬
ible. However, by steric arguments we would predict the stereochemistry
as shown for adduct 103a (endo, exo) rather than adduct 103b (exo, exo)
due to the incursion of extensive van der Waals repulsions between the
methoxy and bridge hydrogens in the transition state for formation of
103b. To rigorously prove the stereochemistry of 103 required the trans¬
formation of the ketal to a carbonyl moiety. It has been reported that
trimethylsilyliodide (TT1S-I) is effective in the hydrolysis of ketals to
66
produce ketones. Treatment of adduct 103 with TMS-I resulted in selec¬
tive demetnylation, producing alcohol 107 v/ith the ketal moiety remaining
intact, presumably due to steric hindrance by the flanking chlorine atoms

63
as well as inductive retardation of initial oxygen coordination to sili-
1 13
con prior to the first deraethylation step. The H and C NMR spectra
of 107 were not significantly changed from that of 103a except for the
absence of the methoxy signal.
When adduct 103 was subjected to cold H^SO^ (cone), clean conversion to
the ketone 108 resulted.^ The fully coupled NMR spectrum of ketone
108 shows no long-range coupling of the carbonyl (6 186.87), thereby
confirming its assigned stereochemistry and that of adduct 103a as endo,
exo.
The stereochemistry of adduct 105 was similarly established to be
the exo adduct of methoxybisesquinene due to the lack of vicinal
coupling (6 2.97, H-1,2, s). Previously, the tetracyclone adduct of
norbornene had been assigned the endo, exo (110a) configuration based
62
principally on the phenyl multiplicity patterns.

64
By analogy, we fully expected the methoxybisesquinene-tetracyclone adduct
to be endo, exo (105b) as well. That this was not the case was clearly
13
demonstrated by the C NMR carbonyl multiplicity (ó 202.7, J=7.0 Hz, t)
which dictates the exo, exo stereochemistry for adduct 105a. Somewhat
62
puzzled by this discrepancy, we prepared the norbornene-tetracyclone
adduct (110) for direct comparison with 105a (see Figure 4.10). The
13
coupled C NMR spectrum of 110 exhibited a triplet for the carbonyl
(6 202.1, J=6.9 Hz), thereby necessitating the reversal of the stereo¬
chemical assignment for the norbornene adduct to 110b (exo, exo).
These results may be explained by considering the facile cyclorever¬
sion which often occurs in some Diels-Alder adducts and has been shown to
equilibrate the kinetically formed endo adducts to the more stable exo
adducts (e.g., maleic anhydride endo adducts equilibrate to exo on heat¬
ing). Additionally, it has been noted that decarbonylation occurs more
readily for endo tetracyclone adducts, presumably due to relief of strain
68
and favored stereo electronic alignment. Since the reaction conditions
promoted extensive decarbonylation, it is conceivable that our results
reflect only the thermodynamic product being isolated. Preliminary
results for the adduction of tetracyclone to norbornadiene at room temper¬
ature indicate that the endo, endo isomer is formed exclusively. If a
chloroform solution of this adduct is warmed, rapid cycloreversion occurs
as evidenced by the purple color. Thus, we must conclude that a delicate
balance exists for the preference of stereochemistry in tetracyclone
adducts, the nature of which is still little understood.

65
Figure 4.10. Carbonyl multiplicity patterns.

66
Suggestions for Future Work
An interesting synthetic application for these bridged ketone
adducts of methoxybisesquinene was suggested by inspection of the mass
spectral fragmentations of adducts 108 and 105a. After loss of CO, the
tetrachloroketone 108 fragments quite readily into tetrachlorobenzene and
a triquinocene derivative (111) (C^H^O, m/z 162, 49% rel intensity).
The tetracyclone adduct 105a behaves similarly with initial loss of CO
(m/z 544, 100% rel intensity) followed by loss of C-^H-^O to produce
^30^22 382, 25% rel intensity) which corresponds to tetraphenylben-
zene. Thus, as outlined in Scheme 4.3, a thermal cycloreversion process
should extrude the tetrasubstituted benzene derivative 112 with concom¬
itant formation of the novel bridgehead substituted tetraquinacene 111.
R
OMe
R= Cl or 2
112
111
Scheme 4.3

CHAPTER FIVE
EXPERIMENTAL
General
Melting points were recorded using a Thomas-Hoover capillary melting
point apparatus and are uncorrected. Analyses were performed by Atlantic
Microlab, Inc., of Atlanta, Georgia.
Proton NMR spectra were run on either a Varían EM-360, a JEOL FX-
100, or a Nicolet 300 spectrometer. Chemical shifts were recorded
relative to tetramethylsilane (TMS) at 6 0.00. After the chemical shift,
values are given in parentheses for the multiplicity of the peaks, the
apparent splittings (J) where applicable, and the relative integration.
The symbols used for multiplicities are: s = singlet, d = doublet, t =
triplet, q = quartet, pent = pentet, and mult = multiplet.
Carbon NMR spectra were recorded on a JEOL FX-100 instrument with
chemical shifts relative to the deuterochloroform reasonance at ó 77.00.
After the chemical shift, values are given in parentheses for the multi-
69
plicity of the peaks as determined by off-resonance or INEPT decoupling.
i 1 s
The symbols used are: s = -C-, quaternary; d = -CH, methine; t = ^CH^,
methylene; and q = -CH^, methyl.
Infrared spectra were recorded on a Perkin-Elmer 283B spectrophotom¬
eter. The KBr pellets were made of the solids, and the liquids were run
neat between NaCl windows.
Mass spectra were obtained either on an Associated Electronics
Industries (AEI) model MS-30 mass spectrometer at 70 eV equipped with a
67

68
Nova Systems 4 computer or on a Nicolet Fourier Transform mass spectrom¬
eter model FT/ms 1000.
Analytical gas chromatography was performed with a Hewlett-Packard
5880A equipped with a flame ionization detector and a cross-linked
dimethylsilicone capillary column (fused silica, 12.5 m x 0.2 mm ID).
The standard temperature program conditions were 80°C (1 min), then
20°C/min to a maximum temperature of 250°C (15 min). All retention times
are reported under these conditions, unless otherwise specified.
Preparative GC was performed with a Varian Associates model A-90-P
utilizing a thermal conductivity detector, and a 10% SE-30 on Chromosorb
W (6 ft x 1/4 in).
70
Flash chromatography was performed as described by Still utilizing
MCB 230-400 mesh silica gel. All solvents were distilled prior to use or
were HPLC grade.
Analytical and preparative thin layer chromatography (TLC or prep
TLC were performed on glass-backed E. Merk TLC plates (silica gel
60 F-254), which were cut to the desired size with a diamond scribe glass
cutter. The spots were visualized either by UV fluorescence quenching or
adsorption of I2. A useful technique for prep TLC staining was to place
a thin strip of filter paper (soaked in an 12/pentane solution) on the
edge of the developed TLC plate. This was covered with a glass plate.
Adsorption of the iodine by the sample on the TLC plate allowed the
selective staining of only a small portion, thereby visualizing the
sample streaks.

69
Synthesis
Preparation of 7,7-Dimethoxynorbornene (30)
The reaction sequences were carried out as previously described to
14
afford 30. Specific details of a sample procedure are given below.
An aliquot of 5,5-dimethoxytetrachlorocyclopentadiene (32, 200 g)
was placed in a Pyrex gas scrubber tube which contained a frit in the
bottom and was fitted with a condenser. The ketal 32_ was heated in an
oil bath (160-170°C) while bubbling a gentle stream of ethylene gas
through solution. After ca. 48 h, NMR analysis of an aliquot indi¬
cated loss of the -OMe peak for 32_ (6 3.30) and two new -OMe peaks for 33
(6 3.50, 3.55). The crude material was purified by bulb distillation
(kugelrohr apparatus available from Aldrich; 95-100°C at 0.2 mm Hg) to
afford 32. as a colorless oil which crystallized at room temperature.
The chlorinated ketal _32_ was dechlorinated by the improved method of
Lap and Paddon-Row^ using sodium/EtOH as follows. A sample of tetra-
chloroketal 32. (5.37 g, 0.021 moles) was placed in a flask equipped with
a mechanical stirrer, ^ inlet, and a condenser. Absolute EtOH (100 mL)
was added followed by the addition of small pieces of clean sodium (ca.
15 g) until no more would dissolve in the refluxing solution (small beads
of liquid Na formed on the surface). The reaction was then cautiously
quenched by the addition of MeOH to consume unreacted Na, and the mixture
was poured over crushed ice. The aqueous mixture was extracted with Et20
(3x100 mL). The combined ether extracts were washed with brine until the
washings were clear, dried (MgSO,), and solvent removed in vacuo to
afford the dechlorinated ketal .30. as a yellow oil (2.15 g, 67% yield, 90%
pure by GC). The ketal was subsequently purified by fractional

70
distillation with a 6 in vigereaux column and reflux head (7-10 mm Pig,
bp 48-54°C, 97% pure by GC).
The Hi NMR spectrum (CDCl^, 60 MHz) contained the following
resonances: 6 6.05(t, J=2.0 Hz, 2H), 3.20(s,3H), 3.15(s,3H), 2.76(m,2H),
2.18-1.68(m,2H), 1.06-0.78(m,2H).
13
The proton decoupled C NMR spectrum (CDCl^ contained the following
6 resonances: ó 132.51(d), 117.94(s), 50.97(q), 48.44(q), 43.37(d),
22.22(t).
The mass spectrum (70 eV) had m/z (% rel intensity): 154(M+,20),
139(15), 123(35), 107(22), 95(15), 91(18), 79(100), 77(22), 59(34),
55(16), 45(22).
Preparation of 5-Trimethylsilylcyclopentadiene (28)
Trimethylsilylcyclopentadiene (28) was prepared as previously
20
described but with the substitution of NaH for Na sand. Freshly
distilled cyclopentadiene (33 g, 0.5 mole) was added dropwise via cannula
to a flask containing NaH (12 g, 0.5 mole) and dry THI (250 mL) which was
fitted with a reflux condenser, magnetic stir bar, and argon inlet. With
each addition, smooth evolution of P^ occurred. When all of the NaH was
consumed, the rose-colored THF solution of sodium cyclopentadienide was
cooled (-10°C to 0°C). To the stirred solution, TMS-C1 (54 g, 0.5 mole,
ca. 63 mL) was added dropwise over a 1 hr period. The ice bath was
removed and the reaction stirred for an additional 3 hr. The reaction
was quenched by the addition of Ho0 (5 mL) (note: a better procedure
would be to use MeOH instead), and the contents of the flask decanted to
leave behind a brown sludge (soluble in H2O) The excess THF was removed
in vacuo (no heat), washed with F^O, and finally extracted into Et20.

71
The Et^O extracts were dried (Na2S0^) and solvent removed in vacuo.
Capillary GC (50°C to 200°C at 10°C/min) indicated two major components:
silane 28. (2.59 min, 47.6%) and an unknown high boiling material
(6.50 min, 33.5%, possibly trimethylsilanol). Pure silane _28^ was
obtained by fractional distillation (11 mm Hg, bp 29°C, 97% pure by GC).
Reaction of 7,7-Dimethoxynorbornene (30) with 5-Trimethylsilylcyclopenta-
diene (28)
Method A: A1C13/CH2C12, -78°C.
To a 50 mL flask fitted with an addition funnel, magnetic stir bar,
O
and N2 inlet, were added dry CH2C12 (10 mL, 3 A molecular sieves) and
AlClg (520 mg, 3.9 mmole). The mixture was cooled to -78°C (dry ice/ace¬
tone), and a mixture of 7,7-dimethoxynorbornene (30, 500 mg, 3.25 mmole)
and TMS-cyclopentadiene (28, 448 mg, 3.25 mmole) was dissoved in 10 mL
dry CH2C12. This was added dropwise to the stirred suspension of AlCl^.
The reaction was quenched after 1.25 hr by the addition of saturated
NH^Cl (20 mL). After allowing the mixture to warm to room temperature,
the organic phase was washed with saturated NH^Cl (2x20 mL), saturated
NaCl (2x20 mL), deionized H20 (2x20 mL), and dried over MgSO^. The
solvent was removed in vacuo leaving a yellow-brown oily residue which
was fractionated on a 2 mm silica gel TLC plate (5% Et20/hexane).
Isolated from the plate as colorless oils were alkenes 39. (106 mg, 17%,
Rf 0.45) and 36 (15 mg, 2.5%, Rf 0.71). All spectral data (vide infra)
were consistent with their proposed structures.
Method B: AlCl3/Et20, 0°C.
Typically to a flame dried 100 mL flask fitted with a septum, mag¬
netic stir bar, and N2 inlet, A1C13 (1.0 g, 7.5 mmole) was added. After
flushing with N3 anhydrous Et20 (40 mL) was added via syringe, and the

72
mixture was stirred at 0°C for 10 min (until AlCl^ dissolved). To the
stirred solution of AlCl^, 7,7-dimethoxynorbornene (30, 1.0 mL,
6.6 mmole) was added dropwise via syringe and allowed to stir for an addi¬
tional 5 min. Next TMS-cyclopentadiene (28, 1.1 mL, 0.89 g, 6.5 mmole)
was added dropwise via syringe. The solution turned light brown after
the addition of the silane. After 3-4 hr, the solution turned very dark
(almost black), and the reaction was quenched by the addition of
saturated NH^Cl (40 mL). The organic phase was separated, washed again
with saturated NH^Cl (2x40 mL), and subsequently dried over MgSO^. The
solvent was removed in vacuo and a brown oil recovered (1.3 g). After
flash chromatography on silica gel (3% Et2Ü/pentane) and further
purification on 1 mm prep TLC, relatively pure 26_ was obtained (15-20%
yield).
Method C: BF^*Et20/CH2CH2, 25°C.
To a solution of TMS-cyclopentadiene (2 mL), 1.62 g, 11.7 mmole) in
CH2CI2 (25 mL, dried over 3 A sieves), freshly distilled BF2*Et20 (1 mL,
7.9 mmole) was added. There was an immediate yellow color upon mixing.
To this mixture, 7,7-dimethoxynorbornene (1 mL, 1.02 g, 6.6 mmole) was
added dropwise. The reaction was quenched after 1.75 hr by the addition
of 25 mL saturated NaHCO^ After separating the phases, the organic
layer was washed twice with brine and dried over MgSO^. The methylene
chloride was removed in vacuo leaving a yellow oily residue. Capillary
GC-MS analysis of the crude oil indicated at least three C-^^jgO isomers
with approximately 45% of the mixture to be 26_, with 5% as _39_, and 8%
to be _38. Fractionation of the crude reaction oil by flash
chromatography on silica gel (5% Et20/pentane) afforded a mixture of
C1oH.^0 isomers in 29% yield.
13 lo J

73
Method D: BF3»Et20/CH2Cl2, 5°C.
To a 100 mL 3-neck flask fitted with a magnetic stir bar, thermom¬
eter, dropping funnel, N2 inlet, and septum was added a solution of
TMS-cyclopentadiene (_28^, 8.97 g, 65.0 mmole) in CH2C12 (25 mL, dried
O
over 3 A molecular sieves). After cooling the solution to 5°C (ice/water
bath), BF3*Et20 (4 mL, 32.0 mmole) was added via syringe. To the stirred
mixture a solution of ketal _30 (5.0 g, 32.0 mmole, in 25 mL CH2C12 was
added dropwise over a 20 min period, while maintaining the temperature
S5°C. After a total reaction time of 1.5 hr at 25°C, the reaction was
quenched by the careful addition of saturated NaHCO^ (20 mL). The
organic phase was separated and then washed with NaliCO^ (2x20 mL), satu¬
rated NaCl (2x20 mL), and dried over MgSO^. After solvent removal in
vacuo, a yellow oil v/as recovered (7.9 g) which was immediately fraction¬
ated by flash chromatography to afford a mixture of isomers _26, _39 and _38
in 55.8% yield (see Table 5.1 for a summary of results). In other experi¬
ments employing Method D, the oily residue was left to stand for a short
period (overnight, 5-10°C). The addition of pentane to the oily residue
(6.91 g) produced a precipitate, which was filtered to afford a pale
yellow solid (1.66 g). This precipitate was seemingly polymeric in
nature, as evidenced by a broadened NMR spectrum, and contained a
large percentage of trimethylsilyl moieties.
Spectral Data for Isolated Products from the Reaction of 7,7-Dimethoxy-
norbornene (30) with 5-Trimethylsilylcyclopentadiene (28) (Methods A-D)
7-Norbornylfulvalene (36)
The NMR spectrum (CDCl^, 60 MHz) contained the following
resonances: 66.35(m,6H), 3.5(m,2H), 1.9-l(m,4H).

Table 5.1. Method D: Fractionation by Flash Chromatography Correlated with
GC Retention Times and Area Percent
28
36
37
26
40
38
39
Fraction
Number
Weight (% Yield)
(1.37 min)
(4.55 min)
(4.87 min)
(5.06 min)
(5.11 min)
(5.19 min)
(5.26 min)
Crude
7.9 g (-)
27.9%
2.5%
3.4%
48.9%
0.35%
4.5%
8.0%
2b
2.11 g (23% rec)
86%
3.3%
-
-
-
-
-
4-5b
(polymerized on
—
30.4%
—
_
_
standing)
ioc
(trace)
-
-
-
13.0%
-
-
71.4%
11C
2.51 g (41.7%)
-
-
-
73.6%
-
3.1%
17.1%
12C
0.85 g (14.1%)
-
-
-
75.9%
0.12%
15.7%
1.9%
13d
(trace)
-
-
45.2 %
17.9%
23.1%
5.4 %
-
14d
0.28 g (4.7%)
-
—
69.9%
0.9%
—
_
a GC conditions 80°C (1 min) to 150°C at 20°C/min
b Pentane
c 5% Et90/pentane
d 10% Et^O/pentane

75
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 7 resonances: 6 168.33(s), 135.44(d), 130.70(d), 125.15(s),
121.39(d), 43.42(d), 23.93(t).
The mass spectrum (70 eV) had m/z (% rel intensity): 156(M+,49),
141(22), 128(100), 115(23), 102(11), 91(7), 78(12), 77(11).
syn-7-Methoxy-7-(1l-cyclopentadienyl)norbornene (37a) and syn-7-methoxy-
7-(1l-cyclopentadienyl)norbornene (37b), ca. (50:50)
The NMR spectrum (CDCl^» 60 MHz) contained the following
resonances: <5 6.42(mult,6H),6.09(t, J=1.7 Hz, 4H), 3.06(m,2H),
2.97(m,2H), 2.95(s,3H), 2.90(s,3H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 19 resonances: ó 145.43(s), 144.11(s), 135.39(d), 133.24(d),
132.71(d), 132.51(d), 132.02(d), 131.20(d), 130.56(d), 129.59(d),
96.01(s), 52.83(q), 52.63(q), 46.88(d), 46.44(d), 41.33(d), 39.72(d),
22.90(f), 22.80(f).
The mass spectrum (70 eV) had m/z (% rel intensity): 188(M+,59),
187(18), 173(20), 160(19), 159(36), 158(11), 157(36), 156(49), 155(44),
154(7), 153(11), 147(35), 145(25), 143(10), 142(18), 141(42), 134(14),
130(17), 129(55), 128(72), 127(19), 123(15), 115(55), 93(50), 91(88),
65(100).
Accurate mass of CloH.,0:
13 io
Caled 188.1201 amu
Found 188.1192 amu
3b-Methoxy-3a,3b,4,6a,7,7a-octahydro-3,4,7-metheno-3H-cyclopenta í a 1pen-
talene (26)
The Hi NMR spectrum (CDCl^, 60 MHz) contained the following
resonances: ó 5.8(t, J=1.9 Hz, 2H), 3.3(s,3H), 2.9(m,2H), 2.64(pent,
J=2.95 Hz, 1H), 2.5(m,2H), 1.7(br s,4H), 1.47(d, J=2.74 Hz, 2H).

76
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 8 resonances: ó 130.36(d), 94.39(s), 62.96(d), 56.43(d),
55.94(d), 54.29(q), 43.96(d), 23.49(t).
The mass spectrum (70 eV) had m/z (% rel intensity): 188(M+,100),
173(10), 160(28), 145(21), 123(91), 108(61), 91(60), 77(30), 65(44).
Accurate mass of C.„H,,0:
13 16
Caled 188.1201 amu
Found 188.1268±0.0009 amu
8-Methoxy-3a,3b,4,6a,7,7a-octahydro-3,4,7-metheno-3H-cyclopenta\a 1pen-
talene (38) (mixture with 26)
The NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: 6 5.96(d,d,d; J=6.0, 2.9, 0.86 Hz, 1H), 5.79(mult,2H),
5.76(d,d; J=2.9, 0.85; 1H), 3.27(s,3H), 3.23(s,3H), 2.87(mult,2H),
2.70(mult,2H), 2.65(mult,1H), 2.48(m,2H), 2.0-1.2(mult).
13
The proton decoupled C NMR spectrum (CDCl^) contained the follow¬
ing 13 resonances (after subtraction of peaks for 26): ó 137.04(d),
129.64(d), 93.57(s), 52.97(q), 50.90(d), 494.22(d), 47.81(d), 45.66(d),
42.30(d), 39.47(d), 39.08(d), 26.02(t), 24.51(f).
The mass spectrum (70 eV) had m/z (% rel intensity): 189(14), 188(M+,
100), 173(14), 160(42), 159(22), 145(41), 129(24), 128(28), 123(68), 122(19),
121(27), 117(21), 115(29), 109(20), 108(45), 95(42), 93(23), 91(69), 79(29),
78(18), 77(33), 67(17), 65(43), 51(20), 45(30), 41(26), 39(41).
Accurate mass of C1oH1£0:
13 16
Caled 188.1201 amu
Found 188.1233±0.002 amu
3b-Methoxy-2,3,3a,3b,4,5,6,6a,7,7a-octahyd ro-1,4,7-metheno-lH-cyclo-
pentaTalpentalene (39)
The '''H NMR spectrum (CDC1„, 60 MHz) contained the following
resonances: 6 6.3(d,d;J=2.6, 5.6 Hz; 1H), 5.6(d,d; J=2.2, 5.6 Hz, 1H),
3.3(s,3H), 2.9(mult,2H), 2.5-1.0(mult,511).

77
13
The proton decoupled ~C NMR spectrum (CDCl^) contained the
following 13 resonances: 6 137.04(d), 129.64(d), 93.57(s), 52.97(q),
50.90(d), 49.22(d), 47.81(d), 45.66(d), 42.30(d), 39.47(d), 39.08(d),
26.02(t), 24.51(t).
The mass spectrum (70 eV) had m/z (% rel intensity): 188(M+,100),
173(13.6), 160(41.8), 145(40.9), 123(67.7), 109(19.7), 108(44.8),
95(42.4), 91(69.1), 77(32.6), 65(43.0).
Accurate mass of C.-H.^O:
13 lo
Caled 188.1201 amu
Found 188.1233±0.002 amu
Preparation of 3b-Methoxy-2,3,3a,3b,4,5,6,6a,7,7a-decahydro-l,4,7-
metheno-lH-cyclopenta[a]pentalene ( 39-112 )
To a standard hydrogenation apparatus was added 25 mL ethyl acetate
and 5 mg 10% Pd-C. The suspension was allowed to equilibrate with stir¬
ring under 1 atm of and a solution of alkene 39_ (61 mg, 0.32 mmole,
in 10 mL ethyl acetate) was added. The reaction was allowed to stir for
4 hr during which time 5.8 mL of 1^ was consumed. The reaction mixture
was filtered through celite, the solvent removed in vacuo, and a color¬
less oil recovered (57 mg, 94% yield). The and ^ C NMR indicated
complete reduction of the double bond.
The NMR spectrum (CDCl^, 60 MHz) contained the following
resonances: 6 3.2(s,3H,-0Me), 2.9-0.5(br m,15H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 13 resonances: ó 95.08(s), 51.90(q), 46.05(d), 44.79(d),
42.97(d), 42.25(d), 42.15(d), 41.67(d), 40.50(d), 28.36(t), 27.78(t),
27.34(t), 23.10(t).

78
Bromination of Methoxybisesquinene (26)
Preparation of trans-1,2-dibromo-3b-methoxy-3a,3b,4,6a,7,7a-decahydro-
3,4,7-metheno-3H-cyclopenta[a]pentalene (26-Br^)
To a flame dried flask, fitted with a rubber septum, ^ inlet, and a
magnetic stir bar, was added a solution of the crude isomer
mixture (405.6 mg, 2.15 mmole) in 10 mL methylene chloride and cooled to
-78°C. A 10% (v/v) B^/Cl^C^ solution was added dropwise via syringe,
while stirring, until a faint orange color persisted. The flask was
removed from the cold bath and allowed to warm to room temperature while
stirring. The solvent was removed in vacuo, and a reddish oil was recov¬
ered (850 mg). Gas chromatographic analysis indicated two major compo¬
nents with retention times of 8.65 min (75.3%), 9.58 min (9.6%), which
were the trans-dibromide 26-Br^ and rearranged dibromide k3_, respec¬
tively. Flash chromatography on silica gel (5% Et20/pentane) afforded
the pure trans-dibromide 26_-Br2 as a white solid (433 mg, 57% yield,
mp 98-100°C) which gave the following spectral data.
The NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: ó 4.53(d,d; J=2.7, J=5.2 Hz, 1H), 4.19(d, J=2.7 Hz, 1H),
3.30(s,3H), 2.85(pent, J=2.7 Hz, 1H), 2.60(mult,2H), 2.20(mult,2H),
2.05(mult,lH), 1.65(mult,4H).
13
The proton decoupled C NMR spectrum (CDC1Q) contained the
following 13 resonances: Ó 96.98, 59.94, 58.33, 58.04, 56.33, 54.78,
53.61, 52.58, 48.69, 44.20, 40.84, 23.10, 22.80
The Mass spectrum (70 eV) had m/z: 348(M+,0.3), 270(14), 269(98),
268(15), 267(100), 237(12), 189(19), 188(58), 187(61), 173(13), 160(15),
159(22), 157(35), 156(34), 155(78), 145(23), 129(36), 128(29), 123(55),

79
121(28), 115(36), 109(33), 108(39), 97(28), 95(25), 93(24), 91(76),
82(49), 80(52), 79(45), 77(38), 71(58), 65(41), 57(35), 55(36), 41(34).
79 79 81
Accurate mass of: C1QH1¿;0 Br„ CloH.¿0 or Br
13 16 2 13 16
Caled 345.9568 amu 347.9547 amu
Found 345.9560±0.0053 amu 347.9549±0.0077 amu
Anal. Caled.
for C^H^B^O
%C
%H
Caled
44.86
4.63
Found
44.94
4.68
Preparation of exo,exo-l,3-dibromo-3b-methoxy-3a,3b,4,6a,7,7a-
decahydro-2,4,7-metheno-lH-cyclopentara]pentalene (43)
Bromination of the C^H^O isomer mixture (54.1 mg) at room
temperature produced a mixture of dibromides (82:18, 26-Br^, and 43,
respectively) which were separated by flash chromatography to afford the
rearranged dibromide 43_ as a colorless oil (33 mg, 33% yield) and 26-Brp
(45 mg, 45% yield). Spectral data for the rearranged dibromide 43 is as
follows.
The NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: 5 4.85(t, J=1.2 Hz, 1H), 4.08(t, J=1.46 Hz, 1H), 3.32(s,3H),
2.85(mult,2H), 2.70(mult,1H), 2.20(d, J=4.5 Hz, 1H), 2.10(d, J=3.0 Hz,
1H), 1.9-0.9(mult,6H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 12 resonances: 698.44(s), 54.43(d), 53.46(q), 51.32(d),
50.97(d), 48.25(d), 45.81(2 peaks?, d), 43.47(d), 42.50(d), 41.52(d),
24.12(t), 22.95(f).
The infrared spectrum (film) contained the following absorption
bands: 2950, 1465, 1300, 1250, 1110, 1025, 1005, 906, 835.
The mass spectrum (70 eV) had m/z (% rel intensity): 348(M+,0.59),
270(14), 269(97), 268(15), 267(100), 189(9), 188(21), 187(36), 159(13),

80
156(30), 155(63), 145(11), 129(27), 128(22), 123(55), 121(14), 117(13),
115(28), 109(17), 108(18), 93(15), 91(85), 79(44), 78(22), 77(41),
71(74), 66(11), 65(53), 51(26), 45(46), 41(36), 39(60).
Accurate mass of C^H^O^^Br^^Br:
Caled 347.9548 amu
Found 347.9642±0.0134 amu
Debromination of 26-6^
The dibromide 26-Br^ (843 mg, 2.42 mmole) was added to a 50 mL
flask and was dissolved with gentle heating in absolute ethanol (30 mL).
To this solution Zn dust (0.5 g, 7.65 mmole) was added followed by
5 drops of glacial acetic acid. The flask was stoppered and immersed in
a warm (50°C) sonicator cleaning bath (Bransonic 220) for 7 min. A GC
aliquot indicated complete loss of 26-Br^. The Zn powder was removed by
filtration through celite, and the solvent was removed in vacuo. The
oily residue was dissolved in pentane, washed with saturated NaHCO^, and
filtered again to remove a white precipitate (ZnCO^?). The pentane was
removed in vacuo to produce pure 26_ (>99% by GC) in quantitative yield.
Reaction of 26 with Trimethylsilyl Iodide (TMS-I)
An oven-dried NMR tube was fitted with a septum and flushed with
argon. A solution of 26_ (+ isomers) (17 mg, 0.09 mmole) in CDCl^
(0.5 mL, dried over 3 K molecular sieves) was added. To this solution
trimethylsilyl iodide (25 pL, 0.18 mmole) was added via syringe. The
sample was incubated 24 hr at 40°C in a thermostated oil bath, and the
reaction was monitored by NMR. After the incubation period, the most
noticeable change in the NMR was the appearance of a new -OMe peak at

81
3.3 ppm. The reaction was quenched by the addition of 2 drops of
methanol saturated with NaHCO^. The solvent was removed in vacuo, and
the residue was taken up in ether. The ether phase was washed with 5%
NaHSO^ (3x5 mL), saturated NaCl (3x5 mL), and dried over MgSO^. The
solution was filtered, the solvent removed in vacuo, and redissolved in
CDC13. Analysis by GC-MS [3% SP2100, 5 ft x 1/4 in, 100°C (2 min) to
300°C at 7°C/min] indicated a mixture of at least 6 components.
Following are the values for the retention times, % relative peak height,
apparent M+, and suggested structures: 11.23 min, 6%, M+ 188, (26);
11.68 min, 24%, M+ 188, (39); 12.97 min, 12%, M+ 174 (hydroxybises-
quinene?); 15.4 min, 6%, M+ 220, unknown?; 19.18 min, 100%, M+ (not
visible), 316-127 = 189 (100%) (26-1); 14.8 min, 8%, M+ 332,
C13H16°(188) + I(127) + 0H(17) = C13H1702I(332).
The major component (26-1) of this mixture was collected by
preparative GC and its structure determined by NMR and MS.
The NMR spectrum (CDC13, 100 MHz) contained the following
resonances: 6 4.7(mult,1H), 6.9 (s,3H), 2.5-1.0(mult).
The mass spectrum (70 eV) had m/z (% rel intensity): (M+ not
visible), 190(12), 189(M+-I,100), 188(11), 157(16), 142(21), 129(16),
128(16), 127(18), 123(30), 117(15), 115(15), 109(60), 108(25), 105(12),
91(49), 80(23), 79(64), 78(18), 77(33), 71(17), 67(20), 66(22), 65(26),
53(13), 51(16), 45(19), 41(31), 39(44), 32(14).
Preparation of exo-1,2-Epoxy-3b-methoxy-3a,3b,4,6a,7,7a-decahydro-3,4,7-
metheno-3H-cyclopentaralpentalene (67)
Typically, a CH2C12 solution (10 mL) containing alkene 26_ (193 mg,
1.06 mmole) was cooled to 0°C and treated with Na2C03 (400 mg, 4 mmole),
purified mCPBA (276 mg, 1.6 mmole) and stirred for 2 hr. After addition

82
of 50 mL pentane, the mixture was washed with 10% NaHSO^ (4x50 mL), 10%
NaHCOg (4x50 mL), saturated NaCl (2x50 mL), and dried over Na2S0^.
Removal of the solvent in vacuo afforded a pale yellow oil (187.6 mg, 87%
yield, 94% pure by GC). The material was further purified by flash
chromatography on silica gel (10% Et20/pentane).
The ^H NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: ó 3.29(s,3H), 3.24(s,2H), 2.68(d, J=3.2 Hz, 2H),
2.25(mult,2H), 2.04(pent, J=3.1 Hz, 1H), 1.65(mult,6H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 8 resonances: ó 94.74(s), 54.48(q), 53.17(d), 51.66(d),
50.29(d), 42.89(d), 39.08(d), 23.24(t).
The mass spectrum (70 eV) had m/z (% rel intensity): 204(M+,69),
189(12), 188(14), 176(17), 175(61), 173(24), 161(23), 148(34), 147(36),
129(33), 128(38), 124(91), 123(68), 121(39), 117(37), 115(34), 109(63),
108(38), 98(48), 97(90), 96(39), 91(100), 81(61), 79(66), 77(55),67(45),
65(43), 55(42), 45(50), 41(52).
Accurate mass of C,„H..,0„:
13 16 2
Caled 204.1150 amu
Found 204.1148±0.0028 amu
Preparation of exo-l-Hydroxy-3b-methoxy-3a,3b,4,6a,7,7a-decahydro-3,4,7-
metheno-3H-cyclopentafalpentalene (64-0H)
In a typical reaction, epoxide 61_ (157.3 mg, 0.771 mmole) was added
in a pentane solution (15 mL) to a flame dried flask fitted with a septum
and a magnetic stir bar. The flask was flushed with argon, cooled to
0°C, and DIBAL-H (1.6 mL, 1.5 mmole, 1 M in hexane) was added via
syringe. After stirring for 1 hr at 0°C, the reaction was quenched by
addition of 15 mL MeOH. The gelatinous aluminum salts were removed by

83
filtration through celite and washed with hot MeOH (3x10 mL). The com¬
bined methanol washings were removed in vacuo and the residue was redis¬
solved in 10% Et20/pentane. Initial clean-up was accomplished by flash
chromatography on a short silica gel column (1 in) eluted with 400 mL 10%
Et20/pentane, 100 mL 10% MeOH/pentane, and 100 mL 20% MeOH/pentane, with
the product eluting in the final fraction. Removal of the solvent in
vacuo produced a colorless oil (124.7 mg, 78.5% yield, 96% pure by GC).
Further purification was achieved by flash chromatography on silica gel,
eluted with 50% EtOAc/pentane.
The NMR spectrum (CDCl^, 100 MHz) contained the following reso¬
nances: ó 3.94(dd,J=2.4 Hz, 7.1 Hz), 3.35(s,3H), 2.58(pent, J=2.9 Hz,
1H), 2.34(mult,2H), 2.22(s,2H), 2.1-1.3(mult).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 12 resonances: 696.84(s), 71.40(d), 59.41(d), 54.53(q),
53.22(d,2 peaks?), 50.19(d) , 46.64(d), 43.81(d), 41.33(d), 37.67(t),
23.24(f), 22.85(f).
The mass spectrum (70 eV) had m/z (% rel intensity): 206(M+,17),
188(3.4), 163(15), 162(100), 147(18), 134(10), 131(39), 130(24), 123(24),
121(18), 109(26), 97(20), 96(34), 91(35), 79(19), 67(17), 65(14), 49(20),
41(25).
Accurate mass of
Caled 206.1307 amu
Found 206.1293±0.0026 amu
Preparation of exo-l-3b-Methoxy-3a,3b,4,6a,7,7a-decahydro-3,4,7-metheno-
3H-cyclopenta[alpentalene Acetate (64-OAc)
In a typical experiment, Et^N (49 pL, 2 equiv) and AC2O (18.4 jjL,
1.1 equiv) were added to 64-0H (36.4 mg, 0.177 mmole) dissolved in

84
G^C^ (2 mL). The reaction was stirred for 10 min at room temperature,
and an aliquot analyzed on the GC indicated no reaction. Addition of
DMAP (1.08 mg, 0.05 equiv) and stirring for 3 hr afforded nearly complete
conversion of the alcohol to the acetate, as indicated by GC. After
solvent removal in vacuo, the residue was dissolved in 5 mL Et20 and
washed with 5% v/v HC1 (3x5 mL), saturated NaCl (3x5 mL) and dried over
MgSO^. Removal of the solvent in vacuo afforded a colorless oil (34.9 mg,
80% yield, 92.8% pure by GC). Further purification was effected by prep
TLC (10% Et20/pentane) to finally recover 64-0Ac (30.5 mg, 70% yield,
97% pure by GC).
The NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: 6 4.80(dd, J=2.6 Hz, J=7.3 Hz, 1H), 3.35(s,3H), 2.55(pent,
J=2.3 Hz, 1H), 2.42(mult,2H), 2.23(mult,2H), 2.01(s,3H),
1.8-1.4(mult,7H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 14 resonances: 6 170.58(s), 96.64(s), 74.56(d), 55.95(d),
54.53(q), 53.27(d), 50.00(d), 47.37(d), 43.81(d), 41.28(d), 34.84(t),
23.15(f), 22.76(f), 21.30(q).
The mass spectrum (70 eV) had m/z (% rel intensity): 248(M+,11.9),
189(31.6), 188(67.0), 162(62.4), 123(36.4), 109(56.1), 108(30.0),
91(41.2), 84(38.9), 79(29.4), 51(28.4), 49(66.1), 43(100), 41(33.0).
Accurate mass of
Caled 248.1412 amu
Found 248.1412±0.0028 amu
Preparation of 1l-Keto-tetracyclo[6.2.1.1^’^.0"’^ldodec-4-ene (66)
To a flame dried flask alcohol 1\_ (127.5 mg, 0.72 mmole) and
CrO^ 2pyr (0.94 g, 3.6 mmole) were added and fitted with a magnetic stir

85
bar and a septum. The flask was flushed with argon and dry pyridine
(5 mL) was added via syringe. After stirring for 1.5 hr, an aliquot on
GC indicated complete reaction. The pyridine solution was poured into
50 mL l^O and extracted with pentane (3x20 mL). The combined pentane
extracts were washed with 10% HC1 (3x25 mL), saturated NaHCO^ (25 mL),
H2O (25 mL), and dried over MgSO^. Removal of the solvent in vacuo
afforded a white solid (120 mg, 95.7% yield, 95% pure by GC). Recrystal¬
lization from pentane gave a white solid (mp 53-57°C, 99% pure by GC).
The ^H NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: 6 5.98(t, J=1.7 Hz, 2H), 2.9(mult,2H), 2.2(mult,2H),
1.8-0.6(mult,8H).
13
The proton decoupled C NMR spectrum (CDC10) contained the
following 7 resonances: 6 216.06(s), 136.61(d), 49.15(f), 48.88(d),
45.12(d), 42.13(d), 22.53(f).
Preparation of anti-ll-Methoxy-tetracyclof6.2.1.l^’^.0^’^ldodec-4-ene (72)
To a flame dried flask transferred to a dry box, alcohol 1\_ (200 mg,
1.14 mmole) and dry NaH (55 mg, 2.3 mmole) were added. The flask was
fitted with a magnetic stir bar and a septum and cooled to -78°C in a dry
ice bath. Dry THF (20 mL) v/as slowly added via syringe to the cold flask
was allowed to stir 1-2 min after which the flask was allowed to warm to
room temperature. Freshly distilled Mel (143 yL, 2.3 mmole) was then
added via syringe, and the mixture was stirred overnight. The contents
of the flask were poured onto ice/H?0 and extracted with ether. After
drying over I'^SO^, the solvent was removed in vacuo to yield a colorless
oil (212.4 mg, 98% yield).

86
The NITR spectrum (CDCl^, 100 MHz) contained the following reso¬
nances: 6 6.04(t, J=1.8 Hz, 2H), 4.3(s,lH), 3.08(s,3H), 2.8(mult,2H),
2.02(mult,4H), 1.74(mult,2H), 1.4-0.9(mult,4H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the follow¬
ing 8 resonances: 6 137.34(d), 85.14(d), 56.29(q), 52.97(t), 48.29(d),
46.49(d), 39.62(d), 29.19(t).
3 6 2 7
Preparation of cis,anti-4,5-Epoxy-anti-tetracyclor6.2.1.1 ’ .0 * Idodec-
11-methyl Ether (73)
A solution of alkene 72_ (212.4 mg, 1.12 mmole) in 15 mL was
cooled to 0°C. After addition of f^CO^ (466 mg, 4.4 mmole) and mCPBA
(290 mg, 1.68 mmole, purified by washing with phosphate buffer), the reac¬
tion was stirred at 0°C for 1 hr, whereupon GC analysis indicated com¬
plete loss of starting material. The reaction mixture was worked up by
the addition of pentane (50 mL) to the solution. The organic phase was
washed with 10% NaHSO^ (4x50 mL), 10% NaHCO^ (4x50 mL), saturated NaCl
(2x50 mL), and dried over Na^SO^. Removal of the solvent in vacuo
afforded a colorless oil (218 mg, 94.8% yield). Gas chromatograph anal¬
ysis indicated 93% purity with all impurity peaks <1%. Previous attempts
at purification on silica gel resulted in decomposition, so the product
was used in subsequent steps without further purification.
The ^H NMR spectrum (CDCl^, 100 MHz) contained the following reso¬
nances: 6 4.2(s,1H), 3.22(s,3H), 3.18(s,2H), 2.56(s,2H), 2.21(mult,2K),
1.82(mult,4H), 1.5-0.5(mult,4H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 8 resonances: ó 85.72(s), 56.38(q), 51.51(d), 48.00(d),
41.08(d), 38.25(d), 28.12(t), 27.63(t).

87
The mass spectrum (70 eV) had m/z (% rel intensity): 206(M',4.8),
149(86.5), 123(20.6), 117(39.2), 109(41.4), 93(48.8), 92(43.3),
91(81.7), 82(43.7), 81(63.0), 79(67.0), 77(40.8), 71(100.0), 67(51.9),
66(44.2), 45(73.2), 41(99.3), 39(59.3).
Accurate mass of
Caled 206.1307 amu
Found 206.1299±0.0024 amu
Preparation of exo-3b-Methoxy-3a,3b,4,6a,7,7a-decahydro-2,4,7-metheno-lH-
cyclopenta[alpentalen-3-ol (65-0H)
To a flame dried flask, fitted with a stir bar, septum and purged
with N2» dry THF (15 mL) and freshly distilled Et(250 yL, 2.4 mmole)
were added. The solution was cooled to 0°C, and n-butyl lithium
(1.5 mL, 1.7 mmole, 1.1 M in hexane) was added and stirred for 10 min.
A solution of epoxide 73. (105 mg, 0.52 mmole) in THF (5 mL) was added
via syringe, the solution was refluxed overnight, and then stirred at
room temperature for 7 days. The brown solution was diluted with 20 mL
H2O, then extracted with Et?0 (2x20 mL). The combined Et20 extracts
were washed with saturated NaCl (2x20 mL), dried over h^SO^, and the
solvent removed in vacuo. After flash chromatography on silica gel (2%
MeOH/C^C^ then 4% MeOH/C^C^), a yellowish oil was recovered (57 mg,
53% yield).
The NMR spectrum (CDCl^, 60 MHz) contained the following
resonances: 54.3(d, J=2.4 Hz, 1H), 3.3(s,3H), 2.6-0.9(mult,13H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 12 resonances: 5 95.62(s), 73.25(a), 53.92(q), 48.73(d),
44.84(d, 2 peaks?), 44.54(d), 43.18(d), 41.28(d), 40.30(d), 31.30(t),
25.24( t), 22.41(t).

88
The mass spectrum (70 eV) had m/z (% rel intensity): 206(M ,3),
150(11), 149(100), 125(22), 124(4), 123(1), 117(14), 109(5), 97(4),
91(12), 79(6), 67(5), 66(2), 65(3), 55(3), 53(4), 45(4), 41(8), 39(5).
Accurate mass of C^2^g02:
Caled 206.1307 amu
Found 206.1306±0.0014 amu
Preparation of 3b-Methoxy-3a,3b,4,6a,7,7a-decahydro-3,4,7-metheno-3H-
cyclopenta[a]pentalene (26-^)
A standard atmospheric hydrogenation apparatus was charged with 20 mL
EtOAc and 50 mg 10% Pd-C. After the stirred suspension was allowed to
equilibrate under 1 atm K^, a solution of 26_ (500 pL, 543 mg, 2.87 mmole
in 10 mL EtOAc) was added. After stirring for 40 min approximately 60 mL
of H2 was consumed. The reaction mixture was filtered through celite, and
the solvent was removed in vacuo to give a colorless oil in quantitative
yield (91% pure by GC). The reduced material was used without further
purification for the next step (reaction with TMS-iodide).
The NMR spectrum (CDClg, 60 MHz) contained the following
resonances: 6 3.4(s,3H); 2.26-2.15(mult,5H); 1.56-1,50(mult,1H).
13
The proton decoupled C NMR spectrum (CDClg) contained the
following 8 resonances: ó 96.93, 54.29, 53.17, 51.36, 48.88, 45.18,
25.05, 23.10.
The mass spectrum (70 eV) had m/z (% rel intensity): 191(M+,46.0),
189(88.8), 188(12.9), 162(45.8), 129(43.1), 123(69.2), 109(100),
96(63.3), 95(53.5), 91(97.4), 81(40.5), 30(39.2), 79(85.8), 77(57.8),
67(75.2), 65(41.0), 55(45.0), 41(78.8), 39(64.1).
Accurate mass of C-^H^gO:
Caled
Found
190.1358 amu
190.134810.0019 amu

89
Preparation of 3b-Hydroxy-3a,3b,4,6a,7,7a-decahydro-3,4,7-metheno-3H-
cyclopenta[alpentalene (96)
In a typical reaction, to a flame dried NMR tube fitted with a
septum, 26-IU (50 yL, 0.26 mmole), TMS-I (50 yL, 0.35 mmole), and
(0.5 mL) were added via microliter syringe. After mixing, the solution
was allowed to stand at room temperature overnight, whereupon NMR analy¬
sis indicated the reaction was complete (loss of -OMe signal). The
reaction was quenched by pouring into 10 mL saturated NaHCO^ and the tube
rinsed with 10 mL Et20. The Et20 layer was washed with saturated NaHCO^
(2x10 mL), 5% NaHSO^ (10 mL, to remove red color of I2), saturated NaCl
(10 mL), dried over MgSO^, and the solvent removed in vacuo. A white
solid was recovered (46 mg, 99.5% crude yield, mp 100-105°C). After
recrystallization three times in pentane, pure alcohol %_ was recovered
(mp 122.5-123°C,19 mg, 41% yield).
The ^H NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: 6 2.35(mult,2H), 2.16(pent, J=2.9 Hz, 1H), 2.00(t, J=2.0 Hz,
2H), 1.85(s,-0H), 1.68(mult,2H), 1.61(d, J=2.68 Hz, 2H), 1.5(mult,6H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 7 resonances: 6 91.55(s), 56.68(d), 54.22(d), 51.29(d),
46.05(d), 25.14(d), 23.15(d).
The infrared spectrum (KBr pellet) contained the following absorp¬
tion bands: 3280 (OH), 2950, 2860, 1295 (C-0) cm-1.
The mass spectrum (70 eV) had m/z (% rel intensity): 176(M ,47.5),
159(1.6), 148(28.4), 133(21.0), 109(29.5), 96(100), 95(77.5), 91(28.9),
81(37.3), 79(32.1), 78(10.1), 77(20), 67(38.2), 55(19.0), 41(22.9).
Accurate mass of C,J,,0:
12 16
Caled
Found
176.1201 amu
176.1195±0.0013 amu

90
Anal. Caled, for Hi6°:
ZC %H
Caled 81.77 9.15
Found 81.60 9.19
g r —j i g
Preparation of Tetracvclo[7.2.1.0 ’ .0 ‘ ldodeca-1-one (98)
In a dry box, potassium t-butoxide (330 mg, 2.8 mmole) was added to
a flame dried heavy walled ampule and sealed with a septum. To the
ampule alcohol (96) (24 mg, 0.14 mmole) was added via syringe (dissolved
sample in 2 mL dry t-butanol, and the flask and syringe were rinsed with
1 mL of fresh t-butanol). The ampule was frozen, evacuated, sealed, and
then placed in a small bomb which contained 1-2 mL of t-butanaol to equal¬
ize pressure. The reaction mixture was heated in an oil bath at 200°C
for 22 hr. After cooling, the reaction mixture was diluted with 5 mL
pentane and washed with water (3x10 mL), dried over MgSO^, and the sol¬
vent removed in vacuco to yield a colorless oil (18.1 mg). Gas chromato¬
graphic analysis indicated two major components: starting alcohol (96)
(5.60 min, 20%) and ketone (98) (6.08 min, 72.3%). A third component
(3.06 min, 5.6%) was unidentified. After prep TLC (15% Et20/pentane on
0.25 mm silica gel), pure ketone (98) (7.1 mg, 30% yield) was obtained.
The NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: ó 2.19(mult,2H), 2.10(mult,2H), 1.90(mult,2H), 18-0.7(mult),
1.45-1.0(mult).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 12 resonances: 6 221.38(s), 61.67(d), 48.36(d), 47.40(d),
45.88(d), 44.06(d), 36.28(d), 34.53(f), 26.75(f), 23.47(f), 23.23(f),
18.15(f).

91
The infrared spectrum (thin film on NaCl contained the following
adsorption bands: 2950, 2875, 1740 (C=0) cm ^.
The mass spectrum (70 eV) had m/z (%rel intensity): 178(1.03,
177(10.36), 176(M+,77.8), 175(7.1), 148(14.0), 147(14.0), 135(10.5),
134(13.8), 133(17.9), 108(24.6), 95(26.3), 91(32.7), 82(23.3), 81(48.7),
80(51.5), 79(36.0), 67(100), 66(43.9), 41(31.6).
Accurate mass of C,„H,,0:
12 16
Caled 176.1201 amu
Found 176.1214±0.0016 amu
Reaction of 26 with Trifluoroacetic Acid (TFA)
To an NMR tube containing 26_ (4.31 mg) dissolved in 0001^(0.5 mL)
and fitted with a septum, TFA was added dropwise via microliter syringe.
As the TFA was added, the NMR was monitored. Very little change was
noted until the addition of about 50 yL of TFA, and the reaction was
allowed to stand overnight. The contents of the tube were rinsed out
with pentane (5 mL) and washed with saturated NallCO^ (3x20 mL), then
saturated NaCl (2x20 mL) and dried over MgSO^. Analysis by GC indicated
complete loss of alkene _26, with two new peaks at 6.11 min (9.3%) and
6.23 min (87.6%). By GC-MS, both peaks had M+ 302. The residue, after
removal of solvent, was purified by flash chromatography to afford a pure
sample of the major component 64-TFA.
The NMR spectrum (CDCl^, 60 MHz) contained the following reso¬
nances: ó 5.0(dd, J=2 Hz, 7 Hz, 1H), 3.35(s, 3H, -OMe), 2.7-2.l(mult, H),
2.0(d, J=7 Hz, 1H), 1.8-1.2(mult, H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 13 resonances: -6 96.50(s), 79.44(d), 55.56(d), 54.68(q),

92
53.56(d), 53.31(d), 49.85(d), 47.56(d), 43.71(d), 41.13(d), 34.40(t),
23.15(t), 22.76(t).
The infrared spectrum (thin film) contained the following absorption
bands: 2960, 1782 (C=0), 1354, 1304, 1220, 1152 cm'1.
The mass spectrum (70 eV) had m/z (% rel intensity): 302(M+,15),
220(5), 205(20), 189(10), 188(8), 174(6), 149(100), 123(10), 117(18),
109(20), 91(28), 79(25), 69(18), 53(10), 44(25).
Preparation of Diels-Alder Adduct (103a)
To an oven dried NMR tube 26_ (106.5 mg, 0.57 mmole) and 5,5-dimeth-
oxytetrachlorocyclopentadiene (102) (113 pL, 0.63 mmole) were added.
After the addition of 0.5 mL C^D^, the tube was flushed with argon,
sealed, and incubated 24 hr in an 80°C oil bath. The course of the
reaction was monitored by NMR (disappearance of the vinyl triplet, with
concomitant appearance of two new -OMe peaks). The contents of the tube
were dissolved in 4% Et20/pentane, and after flash chromatography, a
white solid was recovered (176 mg, 69% yield, GC 14.34 min, 98.8% pure).
Recrystallization from pentane (cooled in dry ice) gave analytically pure
material (mp 128-130°C).
The H NMR spectrum (CDCl^, 100 MHz) contained the following
resonances: 63.57(s,3H), 3.51(s,3H), 3.29(s,3H), 2.64(s,2H),
2.32(d, J=2.7 Hz, 2H), 2.1(mult,3H), 1.56(mult,6H).
13
The proton decoupled C NMR spectrum (C^D^) contained the follow¬
ing 13 resonances: 6 129.11(s), 113.32(s), 96.40(s), 77.40(s), 53.95(q),
52.64(d), 52.15(q), 51.71(d), 51.27(q), 49.32(d), 47.81(d), 45.62(d),
23.24(t).

93
The mass spectrum (70 eV) had m/z (% rel intensity): 419(33),
418(23), 417(95), 416(24), 415(M+-C1,100), 255(28), 253(290, 209(7),
207(7), 123(8), 109(7), 97(21), 96(16), 91(13), 59(17).
Accurate mass (FT-ICR) of ^20^22^'*‘3^3
Caled 415.063453 amu
Found 415.063177±0.0002759 amu
Anal. Caled.
for C20H22C14°3:
07/O
/oC
%H
Caled
53.12
4.90
Found
53.24
4.93
Treatment of Adduct 103a with TMS-I
An NMR tube containing a solution of 103a (18 mg, 0.04 mmole) in
CCl^ (0.5 mL) was treated with TMS-I (30 uL, 0.04 mmole) and the tube
incubated in a 60°C oil bath. The course of the reaction was monitored
by ^H NMR by the disappearance of the -OMe signal (6 3.4). After
7 days, the reaction was worked up as usual (quenched in NaHCO^) and
alcohol 107 was isolated (19 mg, 100% yield, GC 15.54 min, 95.2% pure).
The ^H NMR spectrum (CDCl^, 60 MHz) contained the following
resonances: 6 3.65(s,3H), 3.58(s,3H), 2.70(s,2H), 2.44(d, J=2.7 Hz, 2H),
2.0(mult,3H), 1.8-1.5(mult,6H).
13
The proton decoupled C NMR spectrum (C^D^) contained the following
10 resonances: ó 128.66(s), 91.09(s), 54.97(d), 52.88(q), 52.49(d),
52.39(d), 51.51(q), 48.93(d), 46.20(d), 22.85(t).
Preparation of Tetrachloroketone 108
To a 25 mL round bottom flask, fitted with a magnetic stir bar and a
N2 inlet valve, adduct 103a (93.1 mg, 0.206 mmole) was added followed

94
by precooled (8 mL, concentrated). The flask was stirred in an ice
bath for 5 min, then removed and stirred at room temperature for 15 min,
after which the acid solution was poured over 100 mL of crushed ice. The
acid was neutralized by careful addition of solid NaHCO^ and extracted
with Cl^C^ (3x50 mL). The combined organic extracts were washed with
H2O (2x100 mL), dried over MgSO^, and the solvent removed in vacuo to
yield ketone 108 as a white solid (92.2 mg, mp 123-125°C, GC 12.77 min,
97.6% pure).
The H NMR spectrum (CDCl^, 60 MHz) contained the following
resonances: ó 3.36(s,3H), 2.70(d,2H), 2.55(d,2H), 2,40(rnult,1H),
2.20(br s,2H), 1.60(d,6H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 11 resonances: ó 186.87(s), 128.54(s), 96.31(s), 71.73(s),
54.48(q), 51.73(d), 50.21(d), 49.91(d), 47.52(d), 45.29(d), 22.89(t).
The mass spectrum (70 eV) had m/z (% rel intensity): 404(M+,0.8),
376(5,-CO), 188(4), 163(6), 162(49,CjjH^O) , 161(7), 147(13), 134(8),
131(31), 130(14), 123(8), 121(14), 97(45), 96(100), 91(13).
Caled 403.9904 amu
Found 403.9864 amu
Anal. Caled, for C,QH.¿O^Cl,:
18 16 2 4
%C
Caled
(+3H20)
Found
53.23 3.97
(46.98) (4.82)
46.77 4.43

95
Reaction of Tetracyclone (104) with Methoxybisesquinene (26) to Produce
Diels-Alder Adduct 105a and Diene 106
In a flame dried NMR tube was placed tetracyclone (104) (55.8 mg,
0.145 mmole) and methoxybisesquinene (26) (23.7 mg, 0.145 mmole). The
tube v/as flushed with argon, sealed with a septum, and gently heated with
a small flame to produce a melt. While heating intermitantly for
15-20 min, some bubbling was observed (C0f). The tube was cooled, CDCl^
was added, and a NMR spectrum indicated loss of the vinyl protons.
The mixture was fractionated by prep TLC (1 mm silica gel, benzene) into
two materials; adduct 105a (20.7 mg, 25% yield; mp 215°C dec turns pink
with bubbles) and decarbonylated adduct 106 (54 mg, 68% yield).
Spectral data for 105a
The NMR spectrum (CDCl^, 100 mHz) contained the following reso¬
nances: 6 7.5-6.5(mult,20H), 3.09(s,3H), 2.97(s,2H), 2.58(d, J=2.8 Hz,
2H), 2.39(mult,1H), 2.10(brs, 2H), 173(d, J=2.9 Hz, 2H), 1.55(mult,4H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 18 resonances: 6 202.61(s), 144.34(s), 134.98(s), 134.22(s),
130.06(d), 129.54(d), 127.72(d), 127.25(d), 126.61(d,2 peaks), 97.36(s),
63.66(s), 54.65(q), 52.25(d), 52.02(d), 48.57(d), 45.35(d), 44.65(d),
22.95(t).
The infrared spectrum (film) contained the following absorption
bands: 3060, 2940, 1770(C=0), 1495, 1440, 1305, 905, 725, 690.
The mass spectrum (70 eV) had m/z (% rel intensity): 572(11.7),
546(9.97), 545(41.9), 544(100.0), 384(11.5), 382(25.2), 178(19.3),
123(133), 97(32.6), 96(40.8), 91(15.4), 70(12.8).
Accurate mass of C,„H„,0o:
<+2 36 2
Caled 572.2715 amu
Found 572.2754±0.0043 amu

96
Caled.
for C42H3602:
zc
%H
Caled
88.08
6.34
Found
80.64
6.00
Spectral data for 106
The NMR spectrum (CDCl^, 100 MHz) contained the following reso¬
nances: 6 7.03(s,10H), 6.72(s,10H), 3.39(s,3H), 3.36(s,2H), 2.96(pent?,
J-3.0 Hz, 1H), 2.39(d, J=3.0Hz, 2H), 1.62(d, J=2.7, 2H), 1.50(mult,4H).
13
The proton decoupled C NMR spectrum (CDCl^) contained the
following 18 resonances: ó 142.60, 140.31, 134.95, 134.61, 130.90,
129.25, 127.44, 126.47, 125.69, 124.91, 96.54, 58.43, 54.68, 53.27,
46.30, 45.52, 44.93, 23.15.
The mass spectrum (70 eV) had m/z (% rel intensity): 545(45%),
544(M+,95), 382(35), 372(45), 267(35), 178(15), 167(20(, 149(22),
123(38), 105(100), 97(40), 96(76), 91(45), 77(44), 67(20).
Accurate mass of C
41H36
0:
Caled 544.2760 amu
Found 544.2753±0.0019 amu
Anal caled for C/oKo£0o:
42 36 2
ZC
ZH
Caled
90.40
6.66
(+0.5
H2°)
(88.93)
(6.74)
Found
88.85
6.75

APPENDIX ONE
NOMENCLATURE
The nomenclature of polycyclic hydrocarbons can be quite confusing,
so a short summary is presented here. To complicate matters, Chemical
Abstracts in 1962 adopted its own notation for these polycyclic rings
based upon the lK-cyclopenta[a_]pentalene system.
(0 Ga
Both the Chemical Abstracts notation and the IUPAC notation are given
below for the representative parent ring systems.
3b
y<»*-
T
rS'.
7}
11
X
decahydro-3,4,7-metheno-lH-
cyclopenta[ajpentalene
97

93
decahydro-2,4,7-cetheno-
IH-cyclopenta [a.] pentalene
pentacyclo-
rr . n2,10 n3,7 p.5,9-,
[o.4.0 .0 .0 J-
áodecane
decahydro-1,4,7-iaetheno-
líí-cyclopenta[aJpentalene

99
Trivial Name Derivation: Bisesquinane
Trivial names for complex molecules have been widely used to ease
the burden of reference. Chemists have used their imaginations to derive
these names based on a number of reasons, including natural product
sources (e.g., limonene), structural resemblance to geometric figures
(e.g., cubane), or even derivations of their own names. (For example,
one researcher in a seminar presentation called a compound "george" after
the graduate student who prepared it.) Putting aside the obvious poetic
ring of "griggane" or "grigganol", we opted for the more descriptive name
"bisesquinane", which was derived as shown below.
Starting from norbornane, two compounds have been named sesquinorbor-
nane (lf-norboranes) and bisnorbornane (2-norbornanes). Making the obvi¬
ous fusion of these two systems, we arrive at (bis)(sesqui)(norbornane)
which can be phonetically simplified to "bisesquinane" by extraction of
the underlined characters. An added feature of this name is its refer¬
ence to the 12 carbons contained within this fused polyquinane ring
system [_bi_ (2) x ses (6) = 12].
1
"bisesquinane"
(bi-ses-kwin-ane)

APPENDIX TWO
SELECTED 1E AND 13C NMR SPECTRA

Simulated 300 MHz ‘h NMR Spectrum
39

102
Simulated Decoupled Spectra
39

103
MAJl e

D
Selective Decoupling of ^39
104

SELECTIVE DECGUPLING
39
1
-A_
A.
n I i i i i i i i i 1 1 1 1 r
6.4
6.2
6.0
5.8
BG 97
8/21/82
V
D
C
-T t | t r—|—
5.6 5.4
NORMAL
SPECTRUM
PPM
105

k
o
O'*
or

107

108

lW+3 - S
TOTAL 25
sf=.iII2:j:: -4 h?
ft r í T 7:. 5 1 51 n Z
K T. AIH 6
lift
rfEC.KZ)
FFK *
mis
1
>842.
<8
115.
427
715
?
líe».
52
144.
.11!
213
1
i'r..
Ú
135.
337
315
4
' 'T7
11
133.
,24 3
2 774
5
•>?!.'
S«
132.
787
351?
fi
331S.
99
132.
,512
3327
?
JN5.
79
132.
,324
3333
?
3?P..
84
Ill,
1-3
32 74
•9
3274,
¡ >
113.
. 522
3;li
!0
*«■
, 75
139
,32'
3518
1 l
243 4.
,f. s
«.
.827
732
'1
13.59.
15
73.
287
3714
13
l«8.
c l
77,
.222
4153
14
1852
.89
75
.732
4251
ic
nii
. 14
52
.528
3219
It
im,
,2ó
52,
.211
' 2232
17
¡174
. 21
48
.232
78.1
1C
ties,
, 7.1
48.
443
7314
! 9
i?i«,
.15
â– ! 41.
.372
579
79
ms.
,48 |
41
i :t
:857
?t
9(4
.88
39,
.717
3378
7?
598
.64
21
.378
254
?1
• 573.
,S2
22.
.931
5931
74
.571,
U
22;
224
5353
75
: -1
.27
•1
.853
15 ..3
* d
a
4».
c.
CM
COCI.
<1
-0/1V
imS
4
r**
109

110

{ MeOv,
c.
C7845 . 001
BG246,100MG
0.5ML C0CL3
5MM, GRIGGS
(X
b
â– j i i i | i i i | i i i | i i i | i r
140
120
100
80
60
INEI
HEIGHT
FREQ(HZ)
PPM
C784S .411 ROCCA
1
479.23
9855.22
131.617
4G246.1HHG
2
-54.34
7137.26
94.587
4.5ML CDCL3
3
-19.44
5846.71
77.484
5HH. GRIGGS
4
-22.11
5814.68
77.064
I3C MULTIPLICITY
5
-17.84
5782.69
76.635
6
231.49
4765.57
63.156
. PI* 33.01 USEC
7
458.44
4273.14
56.634
| P2* 16.00 USEC
8
548.94
4236.32
56.142
' D5* 5.10 SEC
9
211.48
4115.63
54.543
If
442.84
333#.37
44.136
Dl VALUES:
1 (« 6.67 NSEC
12
-419.34
1783.83
23.641
1 2* .H USEC
HA • 144
SIZE > 45534
AT » 2.14 SEC
OPD ON â–  1
ABC ON
BUTTERUORTH FILTER ON
OB ATT.» 1
ADC * 12 BITS
AI * 4
SU * */- 2575.25
DO » 44
T<0 = IB USEC
DE* 44 USEC
IL MICH POUER ON
V-t F2* 344 .444 331
BB MODULATION ON
OF» 5333.82
SF» 75.454454
EN= .54
PA= 349.3
PB* -41.2
11.94 NIN
20 '
0
i—r
0 PPM
111

112
Wdd O
L
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REFERENCES
1. L. A. Paquette and M. J. Wyvratt, J. Am. Chem. Soc., 96, 4671 (1974).
2. M. A. Battiste, L. A. Kapicak, M. Mathew, and G. J. Palenik,
J. Chem. Soc., Chem. Coramun., 1536, (1971).
3. G. A. Kraus and J. Tashner, J. Am. Chem. Soc., 102, 1974 (1980).
4. 3. M. Trost and M. Shimizu, J. Am. Chem. Soc., 104, 4299 (1982).
5. 0. Tsuge, E. Wada, S. Kaneraasa, and H. Sakoh, Bull. Chem. Soc. Jpn.,
57, 3221 (1984).
6. D. McNeil, B. R. Vogt, J. J. Sudol, S. Theodoropulos, and E. Redaya,
J. Am. Chem. Soc., 96, 4673 (1974).
7. L. A. Paquette, Aldrichimica Acta, 17, 43 (1984).
tí. R. Bartetzko, R. Gleiter, T. L. Midhard, and L. A. Paquette, J, Am.
Chem. Soc., 100, 5589 (1978).
9. M. A. Battiste and J. F. Timberlake, J. Org. Chem., 42, 176 (1977).
10. R. K. Lustgarten, M. Brookhart, and S. Winstein, J. Am, Chem. Soc.,
94, 2347 (1972).
11. R. K. Lustgarten, M. Brookhart, and S. Winstein, Tet. Lett., 141
(1971).
12. B. Wallace, Jr., Master's Thesis, University of Florida (1977).
13. H. A. Davis and R. K. Brown, Can. J. Chem., 51, 361 (1973).
14. K. E. Baumgarten, ed., Organic Synthesis, vol. 5, New York:
John Wiley and Sons, 1973, pp. 424-28.
15. B. V. Lap and M. N. Paddon-Row, J. Org. Chem,, 44, 1479 (1979).
16. T. Hayashi, K. Kabeta, I. Hamachi, and M. Komada, Tet. Lett., 24,
2865(1983).
17. P. Magnus, Aldrichimica Acta, 13, 43 (1980).
18. W. S. Johnson, P. H. Crackett, J. D. Elliot, J. J. Jazodzinski,
S. D. Lindell, and S. Natarajan, Tet. Lett., 3951 (1984).
135

136
19. A. P. Kozikowski, K. L. Sorgi, B. C. Wang, and Z. Xu, Tet. Lett,,
24, 1563 (1983).
20. C. S. Kraihanzel and M. L. Losee, J. Am. Chem. Soc., 90, 4701
(1968).
21. A. J. Ashe, J. Am. Chem. Soc., 92, 1233 (1970).
22. E. W. Abel and M. 0. Dunster, J. Organometal. Chem., 33, 161 (1971).
23. E. M. Schulman, A. E. Merbach, M. Turin, R. Wedinger, and
W. J. le Noble, J. Am. Chem. Soc., 105, 3988 (1983).
24. V. A. Mironov, E. V. Sobolev, and A. N. Elizarova, Tetrahedron, 19,
1939 (1963).
25. A. Butenandt and J. Schmidt-Thome, Ber., 69, 882 (1936).
26. S. J. Critol and G. W. Nachtigall, J. Org. Chem., 32, 3727 (1967).
27. M. A. Battiste, J. F. Timberlake, L. A. Paquette, C. R. Degenhardt,
J. T. Martin, E. Redaya, T. M. Su, and S. Theodorpulos, J. Chem.
Soc,, Chem. Commun., 941 (1977).
28. A. Nickon and R. C. Weglein, J. Am. Chem. Soc., 97, 1271 (1975).
29. C. A. Grob, Angew. Chem. Int. Ed. Engl., 21, 87 (1982).
30. W. Fischer, C. A. Grob, R. Hanreich, G. v. Sprecher, and A. Waldner,
Helv. Chim. Acta, 64, 2298 (1981).
31. C. A. Grob and P. W. Schiess, Angew. Chem. Int. Ed. Engl., 6_, 1
(1977).
32. P. G. Gassman and J. G. Macmillan, J. Am. Chem. Soc., 91 5527 (1969).
33. P. G. Gassman and J. L. Marshall, Tet. Lett., 2429 (1968).
34. M. E. Jung and M. A. Lyster, J. Org. Chem., 42, 3761 (1977).
35. J. R. Neff and J. E. Nordlander, Tet. Lett., 499 (1977).
36. J. K. Crandall, L. C. Crawley, D. B. Banks, and L. C. Lin, J. Org.
Chem., 36, 510 (1971).
37. J. Haywood-Farmer, H. Malkus, and M. A. Battiste, J. Am. Chem. Soc.,
94, 2209 (1972).
38. W. Steglich and G. Hofle, Angew. Chem., Int. Ed. Engl., _8, 981 (1969).
39. E. M. Engler, J. D. Andose, and P. v. R. Schleyer, J. Am. Chem. Soc.,
95, 8005 (1973).
40. E. Osaw and H. Musso, Angew. Chemie, Int. Ed. Engl., 22, 1 (1983).

137
41. D. Farcasiu, E. Wiskoff, E. Osawa, W. Thielecke, E. M. Engler,
J. Slutsky, P. v. R. Schleyer, and G. Kent, J. Am. Chem. Soc., 96,
4670 (1974).
42. R. R. Sauers, C. A. Weston, and B. I. Dentz, J. Org. Chem,, 45, 2813
(1980).
43. N. L. Allinger, J. Am. Chem Soc., 99, 8127 (1977).
44. N. H. Werstiuk, Tetrahedron, 39, 205 (1983).
45. A. Nickon and J. L. Lambert, J. Am. Chem. Soc., 84, 4604 (1962).
46. J. J. Hurst and G. H. Whitham, J. Chem. Soc., 2864 (1960.
47. A. Nickon, D. F. Covey, G. D. Pandit, and J. L. Frank, Tet. Lett.,
3684 (1975).
48. W. T. Borden, V. Varma, M. Cabell, and T. Ravindranathan, J. Am. Chem.,
Soc., 93, 3800 (1971).
49. 73. F. Chiang, C. F. Wilcox, Jr., and S. H. Bauer, J. Am. Chem. Soc.,
90, (1968).
50. A. Yokozeki and K. Kuchitsu, Bull. Chem. Soc. Jpn., 44, 2356 (1971).
51. A. P. Marchand, Stereochemical Applications of NMR Studies in Rigid
Bicyclic Systems, Deerfield Beach, Florida: Verlag Chemie Int., 1982,
pp. 60-62.
52. C. S. Foote, Tet. Lett., 579 (1963).
53. N. Muller and D. E. Pritchard, J. Chem. Phys., 31, 768, 1471 (1959).
54. K. E. Wibert, et al., Tetrahedron, 21, 2749 (1965).
55. K. Tori, T. Tsushima, H. Tañida, K. Kushida, and S. Satoh, Org. Mag.
Resonance, 6_, 324 (1974).
56. D. G. Garrett, M. D. Ryan, and P. L. Bealleu, J. Org. Chem., 45, 839
(1980).
57. M. A. Battiste, J. F. Timberlake, and H. Malleus, Tet. Lett., 2529
(1976).
58. K. N. Houk, Tet. Lett., 2621 (1970).
59. K. Matsumoto, Y. Kono, T. Uchida, J. Org. Chem., 42, 1103 (1977).
60. L. M. Jackman and S. Sternhell, Applications of NMR Spectroscopy in
Organic Chemistry, London: Pergamon, 1972.
61. J. Haywood-Farmer,
94, 2209 (1972).
Malkus, and M. A. Battiste, J. Am. Chem. Soc,,

138
62. J. M. Coxon and M. A. Battiste, Tetrahedron, 32, 2053 (1976).
63. A. G. Anastassiou, R. L. Elliott, H. W. Wright, and J. Clardy,
J. OrR. Chem., 38, 1959 (1973).
64. R. U. Lemieux, T. L. Nagabhushan, and B. Paul, Can. J. Chem., 50,
773 (1972).
65. R. Y. S. Tan, R. A. Russell, and R. N. Warrener, Tet. Lett., 4175
(1979).
66. M. E. Jung, W. A. Andrus, and P. L. Ornstein, Tet. Lett., 4175 (1977).
67. K. A. Mead, K. Mackenzie, and P. Woodward, J. C. S. Perkin II, 571
(1982).
68. M. A. Battiste and M. Visnick, Tet. Lett., 4771 (1978).
69. D. M. Doddrell and D. T. Pegg, J. Am. Chem. Soc., 102, 6388 (1980).
70. W. C. Still, M. Kahn, and A. Mitra, J. Org. Chem., 43, 2923 (1978).

BIOGRAPHICAL SKETCH
Billy Glynn Griggs, Jr., was born November 1, 1953, in Memphis,
Tennessee. He attended Clarkston High School in Atlanta, Georgia, and
took early admission to DeKalb Junior College. He then joined the
Chemistry Department at Georgia State University and received a Bachelor
of Science degree in 1975. Having an interest in small molecule DMA
interactions, the author joined the research group of Dr. David Wilson at
Georgia State under whose direction he received a Master of Science
degree in 1977. That fall he came to the University of Florida to study
with Professor E. J. Gabbay and enjoy the palm trees. Following
Dr. Gabbay's sudden death in July 1978 he took a brief respite in the
Department of Medicinal Chemistry before he returned to the Department of
Chemistry to begin study with Dr. Merle A. Battiste in 1981.
Mr. Griggs was married to the former Laura E. Wagner in
October 1981, and they subsequently have had two boys, Jesse and Michael,
in March 1983 and 1984, respectively.
139

I certify that I have read this study and that in my opinion it conforms
to acceptable standards of scholarly presentation and is fully adequate,
in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
Merle A. Battiste, Chairman
Professor of Chemistry
I certify that I have read this study and that in my opinion it conforms
to acceptable standards of scholarly presentation and is fully adequate,
in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
William R. Dolbier, Jr. Ls
Professor of Chemistry
I certify that I have read this study and that in my opinion it conforms
to acceptable standards of scholarly presentation and is fully adequate,
in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
William M. Jones
Professor of Chemistry
I certify that I have read this study and that in my opinion it conforms
to acceptable standards of scholarly presentation and is fully adequate,
in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
.LlLcA?^
Wallace S. Brey, Jr
Professor of Chemistry

I certify that I have read this study and that in my opinion it conforms
to acceptable standards of scholarly presentation and is fully adequate,
in scope and quality, as a dissertation for the degree of Doctor of
Philosophy.
Professor of Medicinal Chemistry
This dissertation was submitted to the Graduate Faculty of the
Department of Chemistry in the College of Liberal Arts and Sciences
and to the Graduate School, and was accepted as partial fulfillment
of the requirements for the degree of Doctor of Philosophy.
May 1985
Dean, Graduate School

UNIVERSITY OF FLORIDA
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3 1262 08556 7567