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Samarium diiodide reactions of alpha-oxygenated carbonyls

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Samarium diiodide reactions of alpha-oxygenated carbonyls
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Acetates ( jstor )
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Chelation ( jstor )
Chromatography ( jstor )
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SAMARIUM DITODIDE REACTIONS OF ALPHA-OXYGENATED CARBONYLS
















BY


JEFFREY A. SCHREIER

















A DISSERATION 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

1995





























LD

A































To God,

who makes all things possible















ACKNOWLEDGMENTS



A very close friend once told me that he believed I was a self-made man. In my opinion, he could not be more wrong. In fact, he helped me to develop into the person I am today.

After ten years of college, I have met many people, all of whom have influenced me in some way. I would like to

acknowledge some of the people who have influenced me the most.

First, I would like to thank my research director, Dr. Eric Enholm. I would like to thank him for helping me develop as an organic chemist. He was helpful, resourceful,

patient, and understanding, but everything summed together could not equal the whole. I have grown immensely under his guidance, and I owe him f or that. Special thanks must also go to Dr. Daniel Ketcha, who gave me a jump-start into the program at the University of Florida. without this jumpstart I know I would not have done as well.

my family must be acknowledged next. My parents have supported me mentally, physically, financially, and emotionally. Without this support I would have never been able to achieve this goal. I want to thank my brother, Jerry, who has an outlook on life I can only hope to achieve. He has shown me many good times I could have had with no one









else. I've always looked up to my brother Frank, for no one else works harder and always, "Just does it." I think of him

when I absolutely have to get something done that seems impossible. I am also grateful to my sister. She has helped

me in more ways than she will ever know and her humor will never fail to make me laugh.

Many new friends are found at graduate school. These friends can make the trials of graduate life seem fun. Paul Whitley was one of these friends to me. we spent many long hours working together in the lab and he made them more pleasurable. Additional thanks go to all past and present members of the Enholm group, especially Kevin Kinter. Thanks also go to Mike Cruskie and Mike Terry. All of us could talk chemistry without spilling our beers. Thanks go to all other

chemistry graduate students, and the best of luck to all of them.

I also want to give thanks to a very special friend, my wife. I will never be able to give her enough praise. She

had to put up with times of long working hours, stressful times, and nonstressful times I would spend with my friends.

She was very supportive, and I f eel I owe her a great deal. I hope to repay her with an endless and happy marriage.












iv
















TABLE OF CONTENTS


ACKNOWLEDGMENTS ........................................... iii

ABSTRACT ................................................... Vi

CHAPTERS

1 INTRODUCTION ........................................... 1

2 CHELATION CONTROLLED ALKYLATIONS ...................... 18

3 RING OPENING REACTIONS ................................ 30

4 RING OPENING REACTIONS OF CARBOHYDRATES ............... 48

5 SUMMARY ............................................... 57

6 EXPERIMENTAL .......................................... 59

General methods ....................................... 59

APPENDIX

SPECTRAL DATA ......................................... 91

LIST OF REFERENCES ........................................ 111

BIOGRAPHICAL SKETCH ....................................... 115




















v















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


SAMARIUM DIIODIDE REACTIONS OF ALPHA-OXYGENATED CARBONYLS By

Jeffrey A. Schreier

August, 1995




Chairman: J. Eric Enholm
Major Department: Chemistry


This dissertation investigated the reactivity of

samarium diiodide with a-oxygenated carbonyls. Samarium

diiodide reacted with carbonyls to form a metal associated ketyl anion. This ketyl anion was formed through a direct redox reaction. The samarium(II) iodide is oxidized to a samarium(III) salt, and the carbonyl was reduced to a ketyl anion. Such metal associated ketyl anions have been used for reductive alkylations, ring formations and simple reductions. The goal of this study was to extend the utility of the samarium ketyl anions by examining a-alkoxy keto radical anions.

The first area of study involved the chelation

controlled alkylation of a-hydroxy ketones. Samarium(III) salts have the ability to chelate to oxygen groups. It was


vi









shown that the samarium salts can chelate between the ketyl oxygen and the a-hydroxy group to produce reductive

alkylations in high diastereomeric excess. Often these

reactions were plagued with unwanted side reactions that limit their synthetic utility, but it was the side reaction that led to the next area of study.

The second area of study involved ring-opening reactions, by the ejection of alkoxy groups alpha to ketones. Tetrahydropyran rings were opened by reduction with samarium diiodide. Although it has been shown that strained rings adjacent to a ketone could be opened via the ketyl anion, this was the first example of non-strained ring-openings. Mechanistic studies show that the initially formed ketyl anion is reduced to a dianion by a second equivalent of samarium diiodide. The dianion ejects the a-alkoxy group to leave a samarium(III) enolate. It was also shown that the samarium enolate could be used to form new carbon-carbon bonds in a one-pot reaction.

The third area of study involved the extension of the samerium diiodide ring opening reaction to carbohydrates substrates. Several carbohydrates were derivatized and subjected to the conditions of the ring opening reaction. The reactions needed to derivatize the carbohydrates and the results of the ring opening reactions are described herein.








vii















CHAPTER 1
INTRODUCTION



Radicals can be generated by light, heat or chemical processes.1 Chemical generation of a radical can be an oxidative process or a reductive process.1-5 Oxidative

processes have the advantage of maintaining functional groups that could be synthetically useful later, but they are more restricted in the structure of the initial substrate. In reductive processes, tributyltin hydride (TBTH) and SmI2 are two common reagents used to generate radicals. Using either of these reagents, radicals can be generated on substrates containing a variety of functional groups, such as a halogen,


with tributyltin hydride: 8+

0 nBu3SnH C-OSnBu3
AIBN
R1 R2 80 C, PhH R1 R2
1 2

with samarium diiodide: 5+
0 SM12 '-OSmI2


R1 R2 R1 R2
3



Scheme 1



1






2


double bond, or thio-carbonyl.2 A much less common site for radical generation is a carbonyl function, such as a ketone or aldehyde.

When SmI2 or TBTH/AIBN reacts with a carbonyl, a ketyl is formed (Scheme 1).2 Unlike most radical reactions that remain neutral or nonionic, the ketyl exists as a radical anion, possessing radical and anionic behavior. It is

important to note that ketyls 2 and 3 are obtained by very different mechanistic pathways and possess different chemical behavior. The pathway from 1 to 2 is obtained by a free radical chain reaction, as shown in Scheme 2. Compound 1

proceeds to 3 in a direct redox fashion. Samarium(II) is

oxidized to the more stable samarium(III) species while the carbonyl is reduced, forming the metal-associated ketyl 3.3 The utility of the tributyltin ketyl is too extensive to discuss fully so the remaining discussion will focus on the samarium ketyl anion.



N=N 2 + N2

CN CN CN



+ nBu3SnH 30- + nBu3Sno
CN CN



nBu3Sn* + 0 nBu3SnO

R +R Rv R.Sh" 2
Scheme 2






3


First introduced by Kagan and coworkers as a useful synthetic reagent, samarium(II) iodide continues to show new and useful reactivity in organic synthesis.4,5 Its use to form metal associated ketyl anions has enjoyed a variety of chemical transformations. These transformations include reductive alkylations, ring formations, ring openings, heteroatom abstractions, and pinacol couplings. Each of these transformations will be discussed briefly.
Pinacol coupling of aldehydes(4-*5) and ketones(6-47) can be carried out efficiently with samarium(II) iodide. Kagan and coworkers have shown samarium diiodide reacts with aldehydes and ketones to form pinacols.4c Equimolar ratios of threo and erythro isomers are generally produced. If even a small amount of water or methanol is present, simple reduction to the alcohol will occur instead of pinacol coupling. In the absence of water or alcohols, pinacol coupling occurs in high yields (66-95%). A variety of

functional groups were able to survive the reductive conditions of the pinacol reaction. These groups include cyano, nitro, and carboxylic acids. It is unclear why

competitive reduction does not occur in the presence of a carboxylic acid, since the acid provides a proton source. Analogous to the carbonyl couplings, the Enholm research group has dimerized imines (10-+11).6 Yields range from 63 to 94% (Scheme 3).






4


O HO OH

OP, H2 Sm 2
1/2 min 95%



O HO OH
SII2 SM2

1/2 min 95%
6 \7



O HO OH
2 Sm2

8 24 h 80%9


R R
R R /
H3 SmI2

H
6-12 h
10 \1

Scheme 3



Carbonyls can be reductively alkylated with samarium diiodide. Such alkylations are very similar to a Grignard reaction and are sometimes referred to as the samarium Grignard or samarium Barbier reaction (Barbier was Grignard's graduate adviser). Although there are two different proposed mechanisms bearing the names Grignard and Barbier, the terms samarium Grignard and samarium Barbier only refer to the procedure used to carry out the reductive alkylation (Scheme






5


4,5).7 Regardless of the procedure, either of the mechanisms could operate.


Barbier Tyne


R-X + SmI2 Re + SmI2X


OOSmI2


2 R3 + Sm12 R2 R3


OSmI2 OSmI2


R2 R3 + Re R2k R3
R

Scheme 4




Grianard Tvoe


R-X + SmI2 y Re + SmI2X



Re + SmI2 O R-SmI2


OSmI2

R-SmI2 + R 04l
R2 R3 R2" R3
R


Re + SmI2 R- + SmI2



Scheme 5






6



Reductive alkylation involves the reaction of samarium diiodide, an alkyl halide, and an aldehyde or ketone (See Scheme 6 for examples).1,8 The samarium Grignard procedure allows the halide to react with the samarium diiodide prior


2 eq. Sm12
n-butyl-X 2qS
n-buutlyOH-x
2-Octanone n-butyl OH 15 X Reaction Time Yield
12 tosylate 10 h 95%
13 iodide 12 h 97%
14 bromide 36 h 96%


HO /
CHO

Smi2

(5 85%
16 17



O HO I
Smi2
CH212 55%

18 19


SmI2, 69% 0
BrCH2CH2CO2Et
S m21




Scheme 6






7


to addition of the carbonyl. The samarium Barbier procedure is any procedure in which all reactants are mixed simultaneously or in which the carbonyl is added to the samarium diiodide solution prior to the halide. Often the products from both procedures are the same.

OH

SmI2 -THF-HMPA
1-bromo-2-phenylethane
23 Bn
0


OBn
22 Sml2-THF-HMPA

Styrene OH

24




Sml2 -THF-HMPA Ph
Ph aPh
25 Styrene, 85% OH
25 0O O
26 (83 : 17)



OPO (NMe2)2
OPO (NMe2) 2 SmI2-THF-HMPA N0

methyl acrylate

27 28 (24 : 1)




Scheme 7






8


Recently a few examples of reductive alkylations which show stereoselectivity have appeared in the literature.9 Much of this work was done in the lab of Inanaga. For

example, the reaction of samarium diiodide with 4-tert-butyl cyclohexanone followed by styrene produced 24 over compound 23 in a 98 to 2 ratio. This axial-selectivity is a result of the samarium ketyl preferring to occupy the more stable equatorial position. If l-bromo-2-phenyl ethane is used instead of styrene, the opposite conformation is formed. This must form from a Grignard type attack along the less hindered equatorial axis.9a Diastereoselectivity which

follows Cram's rule has also been observed (Scheme 7).

Inanaga has demonstrated stereoselective alkylations, in which the configuration of the ketyl was fixed through an eight member ring of samarium associated ketyl anion chelated with a neighboring group (Scheme 7).9b

Samarium(III) ketyl anion can be used in ring

cyclization reactions.9c,10 Molander and Etter have shown that the samarium ketyl anion can react with tethered olefins to form five and six member rings. He has also showed one example of an eight member cyclization. Note that the major diastereomer formed in each reaction is that in which the developing radical is trans to the alkoxy group (Scheme 8). The fundamental reasons for this preference have been attributed to several factors which include electrostatic interactions between the negatively charged oxygen and the






9


HO,

n Sml' 30
29 n

n=l 86%(>150:1)
n=2 91%(36:1)


n=3 52%
4


0

SmIq HO n
n

H
31 32

m=1; n=1 90%(>150:1)
m=1; n=2 92%(93:5:2)
m=2; n=2 85%(2:1:1)



Scheme 8












Figure 1

developing methylene radical and stabilizing interactions between the developing radical and the adjacent alkyl substituent.11,12a Further stereochemistry can be predicted






10


by Beckwith's chair (Figure 1). Beckwith has developed a mnemonic device for predicting the stereochemistry of fivemembered cyclizations.12 The major product predicted by Beckwith's mnemonic is formed from the conformer with substituents in the equatorial position.


O O
Sm12, H20 H

CO2Me 77%

4" 33 6 CO2Me
H



OSmI2 OSml2


CO2Me CO2Me

0* 34 #- 35
H



S


N
TBTH/AIBN
C6H6, 800C, 57%

SiMe3
37 SiMe3 3
38

Scheme 9

When a carbon radical is generated adjacent to a strained ring such as an epoxide or cyclopropane, the ring can be opened.2,3 Such ring openings are driven by the relief






11


of ring strain which compensates for the formation of a double bond at the expense of a single bond. In the case of the epoxide, the formation of the alkoxy radical is also compensated by the release of ring strain.13 Once opened the newly formed radical can be used for a variety of reactions. Ring opening reactions are an efficient way to use the ketyl anion for the reactivity of the radical and can be used without the loss of functionality. Note that the ketone 33 is not lost, but regenerated during the reaction. Motherwell has used this process on cyclopropanes to form various bicyclic compounds (Scheme 9).14 In the case of epoxides, the ejected alkoxy radical has a tendency to abstract hydrogens. The hydrogen which is abstracted is normally from a 8-carbon as demonstrated by Scheme 10.15 In the absence of a hydrogen on a 8-carbon, the alkoxy radical can form various

tetrahydropyran rings with an appropriately placed olefin.16


S

N TBTI, AIBN

C6H6, 800C

0 39 40
OH








OH OH

Scheme 10






12




Like the strained ring openings, heteroatoms alpha to carbonyls have been ejected in acyclic compounds. Molander

and Hahn showed that two equivalents of SmI2 in a THF/MeOH solvent system could remove heteroatoms from an a

-heteroketone.17 When R=H (Structure 41), the yield was only 29%, but when R=Ts or COCH2Ph, the yield increased to 94% and 100% respectively.

Since yields increase when the leaving group is more capable of stabilizing both a radical or a negative charge, it is difficult to say definitively how the leaving group is ejected. In the proposed mechanism, the author of this paper suggests the leaving group is ejected as an anion. Note that in this mechanism the initial ketyl formed is protonated prior to reduction to an anion. This avoids the formation of


0
0
2 SmI2/MeOH.
43
OR 41 42

SM12



IOH SM2 OH OH


Y MeOH S I"OR ORO


Scheme 11






13


a vicinal dianion but leaves a carbon anion adjacent to a protonated oxygen, displaying obvious pKa problems (Scheme 11). It was also shown that a-ketobromides could be removed. It cannot be assumed that the mechanism remains the same as for the alkoxy groups (shown above).17a Bromides can be

reduced anywhere on a substrate; however, the alkoxy group must be adjacent to a carbonyl.

The above has been a short review of samarium diiodide chemistry. Each example shown for the various transformations has been the simplest case. Samarium diiodide has been used in very clever syntheses and on highly functionalized and complicated substrates. Carbohydrates are an example of a higher order substrate that can be modified by samarium diiodide. Many of the transformations mentioned above have been carried out on sugars. One of the

transformations, that has been extended to sugars in an elegant way, is the ketyl initiated cyclization.

CO2Me

CHO
44
0
OH TMSO O
1. Ph3P=CHCO2Me O
TMSO O 2. PDC
43 O CHO CO2Me

TMSO"' O 45





Scheme 12






14



CO2Me HO CO2Me

CHO 2eq. SmI2~ 46

TMSO 0 -780C4 : 1 0

44 0o


HO \ V-C2Me
CHO CO2Me
47
TMSO\* 2eq. SmI2 TMSO"17
-780C
45 O 100 : 1



Scheme 12 cont.


Enholm and Trivellas were able to trap the acyclic form of various carbohydrates with stabilized ylides. After

oxidation of the remaining primary alcohol, the substrate could be cyclized by SmI2. All of the cyclization products were found to be enantiomerically pure (Scheme 12).18

Selective deoxygenation of aldonolactones can be

achieved by samarium diiodide reductions.19 All are similar to Molander's a-alkoxy eliminations shown previously. Ester or lactone carbonyls provide the initial ketyl radical anion. Although the mechanisms vary after the initial ketyl formation, a second equivalent of samarium diiodide is always necessary to reduce the radical that is formed to a anion (Schemes 12-14). The anion is often an enolate. The enolate intermediate was used to form new carbon-carbon bonds by Enholm and Jiang.20






15



OH OH

O qO Sm12 /H20


HO 48 OH HO 49



OAC R OAC R

AcO CO2Me SmI2/H20 AcO H
Aco / IAco


OAC CO02Me
50 S




BzO -- O 2 eq. SmI2 BzO'wb0 53

(+)-dihydrocarvone 1)
52 OBz






BzO 0 2 eq. SmI2 OH ( :

BzOOBz (-)-methone BzO'
54



Scheme 13



Care must be taken in selecting protecting groups.

Hanessian et al showed that, although the isopropylidene groups are stable, benzoate groups undergo 1-elimination as

shown in Scheme 14.19a






16




0 0 0 00 0
3 e q S m l 20


o OH O
O 56 0 57




BzO 0 0 BzO O O
3 eq. SmI2

OB z BzO

OBz 58 59



Scheme 14



The following chapters will contain new advances in some of the areas discussed above. Chapter 2 will discuss the use of hydroxy groups to control the stereochemistry of reductive alkylation reactions. a-Hydroxy ketones were reductively alkylated with allyl bromide. The samarium(III) salts,

formed in the reaction, were chelated between the ketyl and the hydroxy group. The rigid structure formed by chelation allowed for diastereoselectivity in the alkylation process.

Chapter 3 describes the development of a hetero-ring opening procedure. The first example of a samarium diiodidemediated opening of a non-strained ring will be described. Intermediate enolates in the ring opening procedure were used to form new carbon-carbon bonds.






17


Chapter 4 shows the application of the samarium diiodide mediated ring opening reaction on complex compounds

containing stereochemistry. Carbohydrate derivatives were treated with samarium diiodide in attempt to produce an atypical ring opening of a sugar.














CHAPTER 2
CHELATION CONTROLLED ALKYLATIONS



The application of metal-associated ketyl radical anions to acyclic stereocontrol problems is primarily a new area for study. Samarium diiodide is an attractive reagent for this purpose for several reasons. First, it can tolerate various unprotected functional groups. For example, unlike anionic alkylations, samarium diiodide mediated alkylations are not sensitive to unprotected alcohols and amines. Secondly, its reducing ability is chemoselective. Reactivity for the

reduction of carbonyls follows the order: aldehyde > ketone >> ester. Halides follow the order I > Br > Cl >> F and a tosylate has about the same reactivity as an iodide.4b,21 Thirdly, samarium(III) salts are highly oxophilic and therefore provide important bidentate chelations for the stereocontrol of alkylations.

Since samarium(III) salts have the ability to chelate, a hydroxy group placed alpha to a ketone could provide an anchor for the samarium associated ketyl anion. A chelation of this type would form a five membered ring as in Scheme 15. The radical center in 61 (Scheme 15) is an sp3 center that rapidly inverts. The inversion rate is rapid enough that it appears virtually planar on the reaction time scale. The rigid structure of the ring will stop rotation about the C118






19


C2 bond. Approach of an electrophile (E) will favor the face of the "flat" ketyl anion 61 that is least sterically hindered. Addition to the ketone produces a new asymmetric center and diastereomers will be produced. The difference in size of the two groups at C1 will determine the ratio of these diastereomers. If chelation is established and the size difference of the groups is large, a diastereoselective reaction will be accomplished.

I I

HO OH
HO 0 HO 0
S / SmI2 \ / E
C1-C2 ClC2 N RsCRC2E
RL R R 'R RL R
60 61 62


Scheme 15


Several c-hydroxy ketones were needed to test the hypothesis of chelation controlled alkylations. The addition of vinyl magnesium bromides to aldehydes followed by treatment with ozone was the shortest route to these compounds (Scheme 16). The first attempt involved the addition of vinylmagnesium bromide to cyclohexane carboxaldehyde (63). This produced 1-cyclohexyl-l-hydroxyl2-propene in a high yield, but the aldehyde produced by ozonolysis (64) rapidly polymerized upon isolation. It

became necessary to use the less labile ketone. The Grignard derived from a-bromostyrene was added successfully to both






20


cyclohexane carboxaldehyde and heptaldehyde. Ozonolysis of the crude product gave a-hydroxy ketones 65 and 67 in good yields.



1. 91%
MgBr
CHO H
CHO 2. 03, 93%* H
63 64 OH


Ph


CHO MgBr Ph

63 2.03 OH
65 85%


0 PhOH


HI. MgBr Ph
H
2. 03 3
66 67 84% O



Scheme 16


Reaction of ketone 65 with samarium diiodide followed by addition of allyl bromide resulted in reductive alkylation (Barbier Method). Thin layer chromatography showed two main products. After careful column chromatography, these products were determined to be 1) diols 68 and 69 as a 140:1 ratio of diastereomers and 2) alcohol 70. This same reaction was repeated using the Grignard procedure. Results are






21


OH



OH 68


OH OH

Ph Smi2

0 Br Ph OH 69
65



Ph OH 70



Type 68+69 68/69 70 SM Mass balance

Barbier 40 140/1 20 40 80%

Grignard 100 120/1 70 (95%GC)



Scheme 17


summarized in Scheme 17. By far, the major product was 68 in which the alcohols are syn on the longest carbon backbone as predicted by the chelation model in Scheme 15. The Grignard method had a higher yield and only slightly lower diastereomeric excess. This procedure was also less likely to form unwanted side products and was chosen as the best method. Compound 67 was then alkylated using the conditions optimized earlier. This alkylation resulted in a 66:1 diastereomeric mixture with a 60% yield.






22


OH OH

C5H11 Ph 2 SmI2 C5H11

OOPh
0
67 71 60% yield 66:1

Scheme 18



It was our initial belief that the Barbier method would be superior to the Grignard method for chelation controlled alkylations. This belief was based on the premise that, by allowing the hydroxy ketone to react with samarium diiodide, chelated structure 61 would be formed prior to alkylation, producing the highest diastereomeric ratio. As predicted the Barbier method did give a higher diastereomeric ratio but also produced significant amounts of side products. A more in-depth study of these side products will follow in Chapter

3.

The second procedure used for chelation controlled alkylation was the Grignard method. This method allowed the halide to react with the metal prior to the addition of the ketone. Optimal conditions were found to be addition of hydroxy ketone 4 min after addition of halide at room temperature with 2.6 eq. of samarium diiodide. Since

diastereoselectivity was still high, chelate 61 must have been established prior to alkylation. This chelation may be a result of advantageous samarium III salts already in the reaction medium, or chelation by the Grignard species upon approach to the carbonyl.






23




At this point it was important to confirm that the major diastereomer produced was the one resulting from chelation control. The observed diastereoselectivity could have resulted from factors other than chelation. Several models have been developed which can be used in predicting the stereochemistry of non-chelation controlled alkylation.22





Nuc Nuc RSH

S

O R, O RI1 OSiR3
M L L



Nuc Nuc RSH


S
R- MO R1 M OSiR3
L

M L L

Figure 2



Each of these models predict the stereochemistry by selecting a particular rotomer and then choosing the preferred approach of the alkylating agent. These models include the FelkinAnh, Cram, and Curran-Giese. Cram's model, which is purely






24


empirical, is unclear in this situation. Cram and Kopecky recognized that some product resulted from chelation.22b Products of this type are termed anti-Cram even though they obey his pneumonic. In situations void of chelation, Cram's rule was shown unreliable in some cases, if the S, M, or L group was a hydroxy or alkoxy group (Scheme 19). In this

situation the Felkin-Anh model is more reliable.22c,d This model predicts that the preferred rotomer is that in which the hydroxy group assumes the L position (Scheme 19) to maximize the a* overlap.22d The alkylating agent would then approach from the side of this rotomer bearing the smallest group. The product predicted by this Felkin-Anh model would be erythro, while the product predicted by chelation would be threo. Giese clearly states that oxygensubstituted radicals adopt the Felkin-Anh model and would also predict an erythro product.22d In order to unambiguously assign the stereochemistry as threo, this product was synthesized by an independent route.





HO OH Ph
72E R




Ph


Scheme 19






25


By retrosynthesis, one could envision a cis diol 71 as arising from one of two olefins, 72E and 72Z. Either olefin could be converted into the threo diol 71, but 72Z was chosen in order to take advantage of the many well established cisdihydroxylation reactions.23 Cis-dihydroxylation of 75Z would give the threo product 76 and cis-dihydroxylation of 75E will give the erythro product 77 (Scheme 20).

Hydrogenation of 71, obtained by the chelation controlled alkylation (Scheme 18), should match compound 76. The

products of both routes to 76 could then be compared by GC and NMR analysis.

O

Ph____2 PPh3 nBuLi
Ph
73 75Z to 75E, 4:1


Prevost
eos HO OH HO OH
AgOAc
2 C6H13 ~"IPh C6H13
12 H H Ph
AcOH/H20 76 77


H2
Pd/Carbon

HO OH
C6H13 Ph
H

71

Scheme 20






26


Olefin 75 was produced by reaction of butyrophenone with the ylide formed by treatment of 1-bromoheptane with

triphenylphosphine and n-butyl lithium. The product obtained by this procedure was a 4 : 1 mixture of 75Z and 75E. The isomeric ratio was determined by 1H NMR and confirmed by GC. The major isomer as determined by 1H NMR was isolated and injected on the GC to insure the E and Z isomers had similar detection limits. It was determined that the Z isomer was the major product by the chemical shifts of the vinylic hydrogen on the two different isomers. This vinylic hydrogen has different chemical shifts for the E and Z isomer (A 0.47ppm).24 This is a result of the phenyl group's ability to deshield the hydrogen only when it is in the cis position. To further insure the 75Z was the major isomer, a NOE difference experiment was performed. Irradiation of the

vinylic hydrogen peak of the major isomer at 5.43 ppm resulted in enhancement of both vinylic methylene peaks. This result supports the z assignment by placing both methylenes in close proximity to the vinylic hydrogen (See Figures 5 and 6 in Appendix).


Percent enhancement was not determined.

(H' H H



H H Ph



Figure 3







27

The isomeric mixture of 75 (ca. 4:1) was fortuitous, for the products after dihydroxylation produced both the threo and erythro isomers (4:1 ratio). With one isomer in excess, GC retention times for both isomers could be determined (See figure 9 in Appendix).

Compound 71 was then hydrogenated and the crude reaction mixture was injected on the GC. The crude reaction mixture was then co-injected with the products obtained by the Pr6vost reaction.23c Co-injection showed that the same two isomers were produced by the Provost reaction as were produced by reductive alkylation. The hydrogenation reaction products were isolated and shown to have identical 1H NMR spectra as the products from the Provost reaction (except for isomeric ratios, see Figure 7 amd 8 in Appendix). This test supports the stereochemical assignment of the major product from the chelation controlled alkylation as threo.


Br6 (P)
Br P(Ph)3 n-BuLi
no reaction
butyrophenone


Scheme 22



A similar procedure was attempted to confirm the assignment of compound 68. Unfortunately, all attempts to add ylide 78 to butyrophenone failed. Even after 4 days of refluxing ylide 78 and butyrophenone in benzene, no olefin product was formed. It is our belief that the ylide is too






28


sterically hindered to react with butyrophenone under these conditions. Despite the shortcoming of an independent synthesis, comparison to 71 strongly support that compound 68 is the threo diastereomer.


OH OH

H Ph Ph
OHOH
79 80

Figure 4

To insure that the diastereoselectivity of the reductive alkylation was not a result of another structural property of ketone 65, it was reduced by NaBH4 and nBu3SnH. Sodium

boronhydride has the ability to chelate, and the reduction was diastereoselective, presumably producing 80 (Figure 4). Tin in much less likely to form any chelate structure, and the nBu3SnH reduction produced a mixture of diastereomers (79 and 80). The fact that nBu3SnH reduction produced both diastereomers shows that without chelation, compound 65 has no inherent structural properties that could be responsible for the diastereoselectivity observed in the reductive alkylations.

Recently a group in Japan published work very similar to the above study.25 Their work involved the chelation

controlled reductive alkylation of ()-3-hydroxy-5-phenyl-2pentanone (Scheme 22). Like the above study, diastereoselectivity dropped with temperature. This study also found






29


that addition of hexamethylphosphoramide(HMPA) resulted in a slight lowering of diastereoselectivity.


OH

CN eCN
SmI2, 0C
OH 82 91% 90:10



\q 81 0
'N OH

ONCO2Et
Sm12, 00C
83 77% 99:1 0

Scheme 22


The role of an alpha hydroxy group in samarium(III) chelation has now been demonstrated. Our work and the work of Kawatsura shows that the a-hydroxy group plays a

templating role in the samarium diiodide-induced reductive alkylation.25 High diastereoselectivity can be achieved without the need for low temperatures, saving in the cost of each reaction. Since the hydroxy group does not need protection, this procedure should save steps in any synthesis with one or more SmI2 alkylations. Finally, this procedure shows the usefulness and diversity of samarium diiodide in synthetic transformations.















CHAPTER 3
RING OPENING REACTIONS OF SAMARIUM DIIODIDE



A major side product of the chelation controlled alkylation was product 70. This product was formed in

varying amounts; sometimes it was the major product. Although conditions were optimized to limit its formation, product 70 would still occasionally appear on GC traces. A search of the literature for similar reactions revealed a paper by Molander and Hahn.17a


0 OSmIn
2 SmI2 H+
Ph Ph

650OH 84


0 H Ph


Ph Allyl Bromide

85 70


Scheme 23

Molander and Hahn showed that two equivalents of Sm12 in a THF/MeOH solvent system could eject a-keto heteroatoms. For a discussion of their work related to this chapter see Chapter 1. Molander and Hahn's conditions and the protocol



30






31


used for chelation controlled alkylations were quite similar. Although our chelation controlled alkylation reaction was carried out in the absence of methanol, the alpha hydroxy group could provide the same type of proton source. This

proton source was a limiting factor for Molander and Hahn. Although an enol was formed in their proposed mechanism, it was unreactive towards electrophilic additions (Scheme 31). In the absence of a proton source the enol would exist as an enolate, which would be more nucleophilic.

In order to better understand the mechanistic aspects of this reaction, the a-heteroatom was tethered to the substrate as shown in Scheme 24. This tethering has an advantage over Molander's non-tethered substrate in that the alkoxide functionality will not be lost. Furthermore, the role of the proton source can be studied since the c-alkoxide group will not provide a proton source. Finally, the tethering has the opportunity to demonstrate the first opening of a nonstrained ring by use of samarium diiodide.

The ejection of an atom(s) adjacent to a carbonyl via a metal-associated ketyl can follow two mechanistic pathways, depending on the reagent used (Scheme 24). It has been
previously shown that, in the case of strained rings (n=0-*l), the ejected atom leaves as a radical, making path A plausible for either metal.13 In other ring sizes (n=2 or more) and in acyclic cases, we will show that path B is preferred in this reaction with SmI2. In this pathway, the ejected atom leaves as an anion. TBTH is unable to reduce a






32


radical to an anion and is therefore limited to path A. Chapter 2 demonstrates that when chelation is possible the metal may assist in the elimination of oxygen and can function in a templating role for the reaction. We might

predict that in the case of samarium, a strong chelate will be established.3 Tributyltin ketyls are less likely to form strong chelates because tin does not have the strong oxophilicity and Lewis acidity of samarium.

6+
SoM

path A: radical
opens ring

6~M 87K >

I M = nBu3Sn"
R1' M = SmI2

86
_M
path B: reduce to R1l y(
anion, then open
ring 88


Scheme 24


For the first time, we will show that a ketyl radical anion can be used to open non-strained rings. Since enolate 88 is formed by the ejection of the alkoxy group, the carbonyl function can be restored on workup, maintaining functionality of the substrate. Furthermore, we will show that this enolate can be used in situ to form new carboncarbon bonds.






33


Materials were needed in order to carry out our investigation. Although, common sized cyclic ethers bearing an a-ketone function are found in, and are useful as intermediates in the construction of many biologically active natural products, surprisingly, almost no general methods for the synthesis of these compounds have been published.26 Moreover, one route we examined required 4-5 steps and produced complex mixtures of diastereomeric intermediates.27 Several other synthetic methods to prepare substituted THP and THF rings are available. Unfortunately, nearly all of these methods required (1) de novo construction of the cyclic ether portion, or (2) a highly strained ring system, or (3) do not afford any direct access to a valuable 2-ketone function.28 We developed a synthetic approach to this class of heterocycles from inexpensive commercial compounds which already contain five- or six- membered cyclic ethers.

The focus of this work was to convert tetrahydrofuran-2carboxylic acid (90, n=l) or tetrahydropyran-2-carboxylic acid (90, n=2) to the corresponding ketones (91, n=l-92), by treatment with of an organometallic species (RM).29 The

carboxylic acids 90 can be prepared from the commercially available alcohols 89 by oxidation with the Jones reagent. Slow addition of 2.5 equivalents of an organometallic species produces the corresponding ketones in good to fair yields (Scheme 25).






34


OH 0 0
Jones Ox. O 2RM
(OH OH R

ne

89 90 91


Product R = M = n= Yield


92 I Li 1 77%


92 MgBr 1 66%


93 nBu Li 1 50%

94 nBu Li 2 45%[a]

95 Li 2 67%


95 MgBr 2 55%


96 ii Li 2 45%


97 Li 2 65%


98 MgBr 2 0%[b)

99 fN Li 2 45%


a. GC yield; isolated 40%.
b. Carbinol was the only product.


Scheme 25


For expensive organolithium species, where use of an excess would not be desired, the carboxylic acid can be






35


converted into the lithium carboxylate prior to alkylation. The carboxylate can then be converted to the ketone with the addition of only 1.1 eq. of the organolithium species. The drawback to this procedure is that it adds one step.

0 M-O O-M 0

OH 2 RM A
OH R R

)nn -M20 n
90 100 91

HD RM

o OH
0 OY
0 RM CR
R a R
R
n
91 101


Scheme 26


In general, the lithium reagents function better than the Grignard reagents, as shown in Scheme 25. The only Grignard reagent to produce reasonable yields of the ketone was phenylmagnesium bromide. The major product for all other Grignard reagents was undesired carbinol. The carbinol 101 (Scheme 26) is a major byproduct in this and related transformations using RLi or RMgX. This adduct forms because ketone 91 is much more reactive than the carboxylate anion to attack by the organometallic species. Therefore, the success of the reaction depends upon the stability of the dianionic






36


alkoxide 100 that is formed. Dilithium adducts(100, M=Li) can be stable in refluxing THF where as most dimagnesiumbromide alkoxides must be kept at temperatures below -1050C.30 The success of phenylmagnesium bromide may result form a stabilization of the dianionic species 100 by the phenyl ring.

The carbinol can also be formed from excess organolithium reagent present during hydrolysis. Water can liberate the ketone faster than it reacts with some

organolithiums. The excess organolithium reagent can rapidly react with the ketone as it is formed. A survey of various literature methods developed to prevent this side reaction, included extended reaction times, quenching with TMSCI, and quenching several small portions of the reaction into ice and HCI.31 we discovered that an extended reaction time and a careful balance of dilution and equivalents of RM affords the desired products in the highest yields with the simplest procedure and clearly reduces the amount of 101 observed.

Thus, a method for the preparation of a-keto five- and six-membered cyclic ethers was developed in anticipation of our subsequent ring-opening reaction. The approach uses commercial carboxylic acids in a reaction with organometals and generally avoids many pitfalls associated with the alkylation. With a supply of a-keto cyclic ethers, testing of the ring opening reaction was begun.

Our studies initiate by addressing the question of whether non-strained ring can be opened by the ketyl radical






37


anion, and by what mechanism. Ketone 94 was treated with SmI2 in the absence of a proton source to produce 104 in 93% yield after work-up. This was, to the best of our knowledge, the first example of a non-strained ring opening of this type. Ketone 94 was also treated with TBTH, but only produced the alcohol 102. This result suggests that the oxygen is being ejected as the anion because SmI2 is capable of reducing a ketyl anion to the dianion; TBTH can not react in this manner. These procedures were repeated on compound 95 with similar results(Scheme 27).


OH
0 0 OH
R M R or: R



R = nBu(102) Ph(103) nBu(104) Ph(105)
M = SmI2 0% 0% 93% 59%
M = nBu3SnH >50% 92% 0% 0%


Scheme 27


A mechanistic rationale which accounts for the success of SmI2 is shown in Scheme 28.11 The first equivalent of SmI2 reversibly reduces the ketone to the samarium ketyl 106 which has two pathways available to it. One path would be

reversible ring opening to give oxygen-centered radical species 109 which would likely favor the closed-ring species 106. Rapid reduction of 109 to 108 by a second equivalent of SmI2 could trap the equilibrium, for dianionic species 108 cannot reclose. This pathway is plausible if the oxygen-






38


centered radical in 109 can be reduced to an anion faster than re-closure to 106, or if it can rapidly abstract a hydrogen atom from the solvent. The other pathway 106-4107 has the radical reduced to diorganosamarium species 107 which then rapidly undergoes P-elimination to 108. Water work up affords the observed product 105, in high yield.

8t 8+
.S-SmI2 8 .-1 SmI 2

0 0
SmI2 Ph ? Ph
95 <
le

106 109

Sm12 Ile- Sm12 le8+ 8- 5+
50.-SmI 2 0 .... M2 6+


Ph Ph- SmI2
I Sm I 105
H20

107 108


Scheme 28


It is interesting to note that when one equivalent of SmI2 is added to 95 under dilute conditions, no reaction occurs after several minutes and 105 is not visualized on TLC. Only after several hours of stirring at room temperature(RT) does 105 form, and only in 6% yield. Recovered starting material was the main product(90%), and 4% of the product resulted from simple reduction of the






39


carbonyl. only when the second equivalent of SM12 is added, does 105 form with high yields. If 109 was present in any appreciable amount after one equivalent, it may abstract a hydrogen atom from THF and form product. The reaction

appears to be driven by the second equivalent of Sm12. The key here may be that a radical species like 109 prefers the closed ring and 107 forms slowly and cannot readily reverse because it is dianionic and 13-eliminates the ether oxygen.

we feel that the preferred path here is via the

dianionic species 107, where the main energy barrier is the two negative charges in close proximity. Several reasonable literature analogies to similar dianionic species exist. Dianionic intermediates like 107 are well -established when they arise from aryl ketones (R1 = aryl) which extensively delocalize the anion32 or where there is a tight ion pair with

some covalent character, such as with M = Li.33 mechanistic tests on the nature of the ejected species will be proposed in the future work section which will help confirm this pathway. In support of the 95-->106-4107-4*108--->105 path we find 1. a strong driving force with the separation of the anionic charges in 107-4108 to open the ring; 2. the oxygen departs but it is activated by the Lewis acidity

(oxophilicity) and coordination of the samarium in 107; 3. the more electra-negative oxygen better supports the negative charge than the carbon; 4. the failure of the less polar and more radical-like tin ketyl also lends support to this






40


anionic pathway, because it cannot form a dianionic

intermediate, like 107.

The tin ketyl 110 shown in Scheme 29 can undergo an equilibrium similar to the Sm12 equilibrium (110<-4111)with the closed form 110 much more highly favored.34 without the

ability to reduce the radical to an anion, as was possible in the SmI2 case above, the more stable radical species 110 eventually reacts with a second molecule of TBTH and produces 112 which upon work up gives 103. We feel tin will be

successful only with strained rings, or with medium and large carbocyclic rings when entropy may favor 111.

8' 8+
Bu3Sn., 0- Bu3Sn.0895 nBu3Sn.

R1 ? R1
110 1ll

Favored disfavored
nBu3SnH nBu3SnH

8+ 8+
Bu3Sn 08- Bu3Sn--O 8/H

H20 R1 R1 H20
103 --H* -- i05

112 113




Scheme 29


With an understanding of the mechanism, conditions were optimized and several examples of the ring opening process






41


were demonstrated.35 In all cases the yields were good. Only entry 116 gave a slightly low yield, but there is some uncertainty that the starting material was pure. The yield of 45% is an average of 45%, 45%, 68% and 30% for the four times the reaction was run.




R .2/.. PA R

H2 0
91

R= yield
104 nBu 70%

105 Ph 98%

114 cHex 81%

115 Bn 72%

116 CH2Hex 45%



Scheme 30


During the ring opening of ketone 91 with SmI2 (Scheme 30), no proton source was present during the course of the reaction and it is unlikely that the entire ring opening process occurred after the quench. In Molander and Hahn's proposed mechanism the ketyl anion was protonated before the radical was reduced to an anion. Thus an intermediate

enolate (108) would be protonated. Once protonated, the enolate can not be used to form new carbon-carbon bonds. For






42


example, a 1:1 mixture of 7-acetoxydodecan-6-one (117) and cyclohexanone under Molander and Hahn's protic conditions produced only cyclohexanone and 6-dodecanone with no addition products (Scheme 31).17a This showed that the enolate is protonated before it can add to cyclohexanone.


0 0
C4H9 C3H7 /M C4H9 C3H7
C3H7 CH

117 OAc 118


Scheme 31


Since the conditions used for the ring opening process contained no proton source, the intermediate enolate 108 should be reactive towards electrophiles. Enolate quenching experiments were designed and implemented with two main goals. The first was to better understand the mechanistic aspects of the reaction by examining the lack of a proton source. Next we wished to take advantage of the intermediate enolate to form new carbon-carbon bonds. All of the above leads to the final and ultimate goal of developing a new synthetic method.




Sm12
cyclohexanone 119
S94 119



Scheme 32






43


The quenching experiments began with ketone 94, which was reacted with 3 eq. of SmI2 (0.1M) at -780C and quenched with dihydrocarvone then warmed to RT. The major product of the reaction was the acyclic form of the ketone 104 but we were encouraged by a 14% yield of the addition product. Cyclohexanone quench produced an addition product along with 104, but was only isolated in a 14% yield (Scheme 32). Adjustment in the amount of SmI2 to 2.6 eq. and increasing the temperature to 0oC improved the yield to 33%. In an

attempt to increase the nucleophicity of the anticipated enolate, HMPA was added but with no marked improvement.36 It became apparent after many failed attempts that the ketone was reacting with the enolate and then undergoing a retroaldol reaction upon work-up. This conclusion was based on observations by TLC. After addition of 94 to the samarium diiodide, TLC showed the ring opening reaction was complete. Cyclohexanone was added and the acyclic dianion of 104 was consumed by TLC and a new product with an identical Rf of product 119 was observed. After workup the main product was, once again, the acyclic compound 104. Alkyl halides were then used to eliminate the possibility of reversibility.

Three alkyl bromides were added to the ring opening reaction to react with the enolate. Since bromide is ejected upon addition to the enolate, reversibility is unlikely. Benzyl bromide, allyl bromide, and crotyl bromide all added to the enolate cleanly. Results are summarized in Scheme 33.






44


The product of addition of the crotyl bromide resulted in a 3 to 1 ratio of E and Z substituted olefin 122.

Ph 0
2.5 eq. SmI2 HO benzyl bromide Ph
86% 120



0 2.5 eq. SmI2
Ph HO
allyl bromide Ph
ev 94 70% 2


2.5 eq. SmI2
Doo
crotyl bromide
65% HOP

122


Scheme 33


Since chlorotrimethylsilane prefers to O-alkylate, it was used as a quench to trap the enolate. The reaction

produced a single product by TLC which decomposed on a silica gel column to produce a lower Rf compound. Proton NMR showed the product to be the TMS derivative 124 (54%, Scheme 34). With the known instability of TMS enol ethers on silica gel,37 it is likely that the insoluble higher Rf compound was the TMS enol ether 123. Other isolation means will have to be implemented to confirm this hypothesis. This result shows a difference in reactivity of the two anionic sites and may prove useful in cases below.






45



Ph SmI2, THF, HMPA TMS Ph
--I- Ph
TMSC1 124

95 TMS /,silica gel

123 Ph
TMSO


Scheme 34


Phenyl tetrahydrofuran-2-yl ketone (92) was prepared from commercially available tetrahydro-2H-furan-2-carboxylic acid. The reaction of 92 with SmI2 produced one major product by TLC prior to a water quench. After quench and

work-up the product decomposed to a complicated and



2 SmI2 H

H20
92 125
H



126 127


Scheme 35


inseparable mixture. The expected side reaction involving the attack on the ketone by the primary alcohol or alkoxide in this basic solution may be responsible for some of these decomposition products (see Scheme 35). In an attempt to






46


prevent this, the reaction mixture was quenched with TMSC1. It was hoped that the TMSCl would protect the alcohol and prevent it from attacking the ketone. This procedure still resulted in an inseparable mixture.



P,,,Ph SmI2, THF, HMPA

128 isopropanol 129


Scheme 36


With some success using the ketones above, the phenethyl ester 128 was prepared from the carboxylic acid. This ester was then treated with SmI2 in THF at 00C, to produce no change by TLC. The reaction was warmed to room temperature but remained very sluggish and addition of HMPA was necessary to increase the reaction rate. After consumption of the starting material by TLC the only insolated product was phenethyl alcohol. It was assumed the phenethyl alcohol was ejected as an anion from the ketyl or dianionic species for purpose of charge separation. In an attempt to trap anionic intermediates, isopropanol (4eq.) was added as a proton source. After the starting ester was consumed by TLC the reaction was worked-up to produce phenethyl alcohol and isopropyl tetrahydropyran-2-carboxyate 129, a simple transesterification (Scheme 36). We believe this transesterification was catalyzed by the Lewis acidity of the samarium diiodide. To prevent any transesterifications, the






47


cyclohexane ester was made and cyclohexanol was used as the proton source. Again under identical conditions no reaction occurred after 24 h. For now, esters remain a limitation in these reactions.

Ring openings using the ketyl anion have never before been accomplished on non-strained rings. This alone provides a new and interesting procedure expanding the realm of Sm1l2 in the field of organic chemistry. This procedure also

provides for carbon-carbon bond formation, by making use of the intermediate enolate. Although many of the examples for this procedure are performed on simple substrates, the scope and limitations are fairly well defined. Furthermore,

samarium diiodide is relatively tolerant to many unprotected functional groups. Therefore, this procedure should prove useful for the synthesis of complex organic compounds.















CHAPTER 4
RING OPENING REACTIONS OF CARBOHYDRATES



The success of the ring opening process described in Chapter 3 prompted an attempt to open rings with a higher order of sophistication. For many years carbohydrates have played a major role in the chiral pool.38 The high degree of oxygenated functionality of the carbohydrates provided chemists with chiral starting materials for synthesis of complex and chiral products.38 This dense functionality also produced a challenging test for the samarium diiodide ring opening reaction.


OH OH OH


O OH OH 0 0 OH

OH HO "o HO "OH
OH OH OH
130 131 132


Scheme 37

Sugars in their natural form exist in a tautomeric equilibrium between the open chain form and the closed chain form. This equilibrium (also called mutarotation) results from the breaking and reforming of the Ci-O ring bond (Scheme 37). Mutarotation epimerizes the anomeric center of the



48






49


sugar.39 In contrast, the samarium diiodide mediated ring opening of a sugar is not reversible and no epimerization will occur. The bond that is cleaved is not Cl-O ring bond, but the C5-0 ring bond. There are very few reactions that cleave the C5-0 ring bond of a carbohydrate. The most wellknown reaction of this type is the Ferrier reaction.40 Herein, we propose a totally new approach to this bond cleavage. In addition to cleaving the C5-0 ring bond, the samarium diiodide mediated ring opening proceeds through an intermediate enolate. This enolate should be reactive towards electrophiles, as discussed in Chapter 3. The chiral nature of carbohydrates and the possible chelate structure of 135, might provide for enantioselective electrophilic additions (Scheme 38).




0 0

*OR R OR
RSM12, E+ OH

RO OR

133 OR %SmI2 E+ OR 134
OR





RO OR
OR 135


Scheme 38






50




One objective of the ring opening reaction was to determine the fate of the enolate intermediate 135. After water work-up (E = H), three possible products could be envisioned. The water could protonate compound 135 to produce the hemiacetal 134 (E = H, Scheme 38), or the hemiacetal may be cleaved to produce aldehyde 136 (Scheme 39). A third, and less fortunate product, 137, could occur by P-elimination of an alkoxy group (OR). P-Elimination was observed by Hanessian et al., when performing similar chemistry on different sugar derivatives (See Scheme 14 in Chapter 1). Hanessian showed that although benzoates

eliminated readily, isopropylidenes where much more reluctant to eliminate.19a Thus it was not clear what might occur in our case.
0
0
R/


OR
R H20 OR 136

RO '1R 0
OR 0

0
135 R

'OR

OR 137


Scheme 39






51


Two sugar derivatives were initially selected to test the ring opening procedure (142 and 145). Protecting groups were placed on all free alcohols to reduce the polarity of the products, rather than to prevent reactions of the samarium diiodide with the alcohols. Typically, samarium diiodide reactions are not sensitive to the acidity of alcohols. Isopropylidenes were used as these protecting groups when possible to reduce the chances of O-elimination.


OH OH
-OH OMe 0 OMe
a ~ b H

HO OH o0o
138 139 140



OH 0

meOMe
Ph d Ph




x( 141 x 142


a) acetone/methanol/HCl (50%). b) Swern Ox. 73%
c) PhMgBr, 72% d) Swern Ox. 71%.


Scheme 40

The first sugar derivative used was ribose ketone 142. This derivative was produced in 4 steps from ribose as shown in Scheme 40. Both protecting groups were installed in one step by a known procedure to produce 139.41 Compound 139 was






52


oxidized by CrO3/Pyridine to produce 140, but only in 40% yield. The Swern oxidation was found to be superior and produced 140 in much better yields.23a Compound 141 was

produced by adding 140 to a solution of phenylmagnesium bromide. Oxidation to ketone 142 was performed by a second Swern oxidation in which excess Swern reagents were used. Although no five member rings were opened in Chapter 3, it was hoped that the ejection of the methoxy group at the anomeric center would prevent the formation of the anticipated ketol elimination product seen in Scheme 35.




OH OH
0 'sOH 0
Acetone 1. Swern Ox.
H2S04/CuSO4 .1 2. PhMgBr
HO 30%0
OH 0
OH
130 143

0
OH
0o 0

Ph" d 1 Swern Ox. Ph OK

aK 60% 3 steps

0 144 145




Scheme 41

The second substrate targeted for the ring opening process was galactose derivative 145. This compound was

produced by four steps similar to those used to form 142.






53


The aldehyde formed by the Swern oxidation was not isolated but reacted with phenylmagnesium bromide immediately after formation. Aldehydes of this type are difficult to purify by chromatography and are often unstable at distillation temperatures.

Compound 142 was treated with SM12/HM~PA. The general procedure called for the addition of the starting ketone to the Sm12/HMPA. Before the entire amount of 142 was added, the samarium diiodide's blue color changed to an unusual orange. This color remained after the addition of water, eliminating the possibility that the color resulted from anionic species. The crude 1H NMR showed only unreacted starting compound 142. This is an unusual result because the

samarium diiodide was consumed. This suggests that the

product of the initial reaction, reacts faster with samarium diiodide that the starting ketone. The reaction was repeated

at a lower temperature (-780C) to reduce the reaction rate. Methanol was also added to quench anions as they were formed to prevent intermolecular anionic reactions. After one hour

at -780C, only a small amount of 142 was consumed as determined by TLC. The reaction was allowed to warm to room temperature and the dark blue color faded to yellow. Half of

the starting material was consumed to produce what appeared to be the pinacol of 142. The pinacol assignment is based primarily on MS showing a formula weight of 558 mmu. This

result was quite unexpected, for pinacol products had never been observed in any previous ring-opening reactions and the






54


presence of methanol should have prevented the pinacol formation as discussed in Chapter 1. It was difficult to speculate why the ring did not open. One possibility is that the isopropylidene produces steric hindrance that reduces the rate in which samarium diiodide can reduce the radical ketyl anion to a dianion. Reducing the rate of the second samarium diiodide reduction would help explain the formation of a pinacol product. A second possibility may be that the isopropylidene enforces the bicyclo[3.3.0] ring system and restricts the opening of the furan ring. This possibility would not explain why the ketone is not reduced to the dianion. In the presence of methanol, one would expect the simple reduction of the ketone to an alcohol to be a major product. No such reduced products are observed. Since

simpler furan rings did not produce open ring products in Chapter 3, furan rings may simply be a limitation of this procedure. In this light, focus was shifted to the pyranose sugars.

Pyranose sugar derivative 145 was prepared for the samarium diiodide mediated ring opening reaction. Unfortunately, this substrate was insoluble in THF. The

limited solubility of this substrate made it incompatible with the conditions needed for the samarium diiodide mediated ring opening reaction. A second pyranose sugar derivative was made. Benzyl groups replaced the isopropylidene in the hopes of increasing the solubility in THF. The anomeric

center was removed to reduce the number of mechanistic






55


pathways the ring opening reaction could follow. The

anomeric center was removed by opening the bicyclic ring structure of 147 with phenylthiotrimethylsilane.42 The

product of this opening contains a C1 phenylthio group and a TMS group on the C6 alcohol. The TMS group was removed with K2CO3 in anhydrous methanol to yield 148. The thioglucoside 148 was removed by reduction with nBu3SnH. The total

synthesis of this substrate is shown in Scheme 42.


O O
Corn heat BnBr/NaH
Starch .H
HO.OH BnO OBn

OH OBn
146 147


OH OH
1. TMS*SPh/TMS*OTf 0 SPh nBu3SnH/AIBN

2. MeOH/K2CO3 BnO" OBn BnO" "'OBn


OBn OBn
148 149


OH
O 0
1. Swern Ox. Ph Swern Ox. P
2. PhMgBr.. .
2. PhMgBr BnO" OBn BnO" "OBn

OBn OBn
150 151


Scheme 42






56


Compound 151 was treated with the identical ring opening conditions as described in Chapter 3. A major product was

isolated from the reaction mixture. Although additional

structural data is needed, an 1H NMR indicated a successful ring opening reaction (Scheme 43). The spectra appears to be consistent with the acyclic structure 152. Compelling

evidence for 152 is the 0.6 ppm upfield shift of the methine peak. The ejection of the oxygen attached to C6 would produce a shift of this nature. The integration of the peak

areas also supports 152 and suggest that A-elimination did not occur (Scheme 43).


/ 34ppm 2.8 ppm
H H" OH

Ph ""SM12/HMlvPA PhH


BnOW'~ "OBn BnO%' 'OBn

OBn 151 OBn 152


Scheme 43

Encouraging, but in need of further investigations, these experiments take the first step towards applying the ring opening process to complex molecular structures. Eventually several carbohydrates will be examined as well as

various electrophiles (E+, Scheme 38). In time, samarium diiodide may prove useful for ring openings of very complex systems.















CHAPTER 5
SUMMARY



The goal of extending the utility of samarium diiodide for synthetic transformations of a-oxygenated carbonyls was achieved. The mild conditions of samarium diiodide reactions and its tolerance of functional groups provide chemists with an ever-growing supply of synthetic transformations. This study describes two of these transformations.

The first new transformation involved the chelation controlled alkylation of carbonyls. a-Hydroxy carbonyls were alkylated with high diastereoselectivity. The diastereoselectivity was controlled by chelation of the metal

associated radical anion with the hydroxy group. Although this reaction proceeds in high yields with high diastereoselectivity, it is in competition with the ejection of the hydroxyl functionality. The ejection of the hydroxy group has its own synthetic utility.

The second new transformation in this study described non-strained ring opening reaction by use of samarium diiodide. Samarium diiodide has the reductive potential to reduce a carbonyl to a dianion. The close proximity of the dianions can drive the ejection of alkoxy groups. When the alkoxy groups are tethered to the substrate their ejection results in ring-opening reactions. Several six-member ethers 57






58


were opened with high yield. Five membered ethers may have opened, but produced too many side-products for complete characterization. These studies show that the carbonyl must be a ketone. When an ester was used as the ketyl precursor, the ester was transesterified or saponified by the Lewis acidity of samarium diiodide.

Carbon-carbon bonds could also be formed during the ring opening reaction. An intermediate of the ring opening reaction was a samarium(III) enolate. It was shown that activated electrophiles would react with these enolates to form new carbon-carbon bonds. It was also shown that 0alkylation can occur during the ring opening process. Oxygen vs. carbon-alkylation was determined by the electrophile, since all other conditions remained the same.

The transformations described in this dissertation result from the unique reactivity of samarium diiodide with an a-oxygenated carbonyl. The metal associated ketyl anion displays both radical and anionic character. This study

explores some characteristics of both the anion and the radical. Furthermore, this work examined samarium diiodide's unique ability to form dianions under mild conditions. This and other studies, continue to demonstrate that samarium diiodide is a synthetically useful reagent.














CHAPTER 6
EXPERIMENTAL


General Methods


Infrared spectra were recorded on a Perkin-Elmer 1600 FT IR spectrophotometer and are reported in wave numbers (cm-1). 1H Nuclear magnetic resonance spectra were recorded on a Varian VXR-300 (300 MHz) and General Electric QE-300 (300 MHz) spectrometer. 13C NMR spectra were recorded at 75 MHz on the above mentioned spectrometers. Chemical shifts are

reported in ppm downfield relative to tetramethylsilane as an internal standard.

All reactions were run under an inert atmosphere of argon using flame dried apparatus. All yields reported refer to isolated material judged to be homogeneous by thin layer chromatography and NMR spectroscopy unless other stated other wise. Solvents and reagents were dried according to established procedures by distillation under inert atmospheres from appropriate drying agents. Tetrahydrofuran2-carboxylic acid, tetrahydropyran-2-methanol, PhLi and nBuLi in hexanes were obtained from Aldrich Chemical Co. Benzyllithium was prepared from toluene using the method described by Eberhardt and Butte.38 All other lithium





59






60


reagents were prepared by slow addition of a halide to excess Li metal in ethyl ether at -400C.

Analytical TLC was performed using Kieselgel 60 F-254 precoated silica gel plates (0.25 mm) using uv light or phosphomolybdic acid in ethanol as an indicator. Column

chromatography was performed using Kieselgel silica gel 60 (230-400 mesh) by standard flash chromatographic techniques.


2-Cyclohexyl-2-hydroxv-l-Dhenvl ethanone (65)


To a solution of 1-magnesium bromide ethenyl benzene (6.6 mmol in 8.5 mL of THF) was added cyclohexane aldehyde (0.93 g, 6.6 mmol) dropwise at 00C. After complete addition the reaction was warmed to room temperature (RT) and stirred for 1 h. The reaction was quenched with NH4C1 (aq, Sat), washed with NaCl (aq, Sat) and dried over Na2SO4. Removal of the solvent under reduced pressure yielded a yellow oil (1.43 g, 100%). The crude oil was subjected to a stream of ozone at -780C in CH2C12 (70 mL) until the solution turned blue. Dimethyl sulfide (1 mL) was added and the solution was warmed to RT. The solution was washed with water, and dried with Na2SO4. Removal of the solvent under reduced pressure gave a yellow oil. Crystallization of the oil from methanol gave 65 as a white solid (1.22g, 85%): Rf = 0.57 (35% THF-hexanes);
mp 89-900C; 1H NMR (CDC13) 8 7.95-7.25 (m, 5 H), 4.95 (dd, 1 H, J = 6.6, 2.2 Hz), 3.62 (d, J = 6.6 Hz, 1 H), 1.86-0.90 (m, 11 H); 13C NMR (CDC3) 8 202.1, 133.8, 128.8, 128.44, 77.24,






61


42.6, 30.2, 26.5, 25.8, 24.8; IR (KBr) 3418, 2933, 2852, 1678, 1597, 1449, 1273, 1217, 1109, 830, 620 cm-1.

Anal. Calcd. for C14H1802: C, 77.03%; H, 8.31%. Found: C, 76.83%; H, 8.32%.


2-Hydroxy-1-phenyl-1-octanone (67)


To a solution of 1-magnesium bromide ethenyl benzene (9.7 mmol in 15 mL of THF) was added heptaldehyde (0.99 g, 8.7 mmol) dropwise at 00C. After complete addition the reaction was warmed to RT and stirred for 1 h. The reaction was quenched with NH4Cl (aq, Sat), washed with NaCl (aq, Sat) and dried over Na2SO4. Removal of the solvent under reduced pressure yielded a yellow oil (1.98 g, 100%). The crude oil was subjected to a stream of ozone at -780C in CH2C12 (70 mL) until the solution turned blue. Dimethyl

sulfide (1 mL) was added and the solution was warmed to room temperature (RT). The solution was washed with water, and dried with Na2SO4. Removal of the solvent under reduced pressure gave a yellow oil. Column chromatography of the oil yielded 68 as a clear and colorless oil (1.6 g, 84%): Rf = 0.55 (35% THF/hexanes); 1H NMR (CDC13) 8 7.9 (m, 2 H), 7.6-7.4 (m, 3 H), 5.1 (m, 1 H), 3.7 (d, J = 6 Hz, 1 H), 1.9-1.7 (m, 2 H), 1.6-1.1 (m, 8 H), 0.85 (t, J = 7.5 Hz, 3 H); 13C NMR (CDC13) 8 202.1, 133.8, 128.8, 128.5, 73.1, 35.9, 31.6, 28.9, 24.9, 22.5, 13.9.






62


Tyoical Barbier Method for reductive alkylations


A solution of allyl bromide (0.9 mmol) and 65 (0.3 mmol, 1 mL THF) was added slowly to SmI2 (1.3 mmol, 0.1 M THF). The reaction was stirred at RT. After stirring for 10 min, the dark blue color of the SmI2 faded to green. The reaction was diluted with ethyl acetate and HC1 (1 mL, 0.1 M) was added. The layers were allowed to separate and the organic layer (1 gL) was injected in the GC. The layers were

separated and the organic layer was washed with NaHCO3 (aq, sat) and NaCl (aq, Sat). The solution was dried over Na2SO4 filtered and reduced under vacuum. Column chromatography of the residue produced unreacted starting material (32%); compounds 68 and 69 (32%, 140:1 ratio as determined by GC); and 5-Cyclohexyl-4-hydroxy-4-phenyl-l-pentene (70; 16%). 5-Cyclohexyl-4-hvdroxy-4-phenvyl-1-Dentene (70)


1H NMR (CDC13) 8 7.4-7.1 (m, 5 H), 5.5 (m, 1 H), 5.1 (m, 2 H), 2.7 (dd, J = 5, 13 Hz, 1 H), 2.4 (dd, J = 6, 13 Hz, 1 H), 2.0 (s, 1 H), 1.7-0.9 (m, 13 H); 13C NMR (CDC13) 8 146.4, 133.5, 127.9, 126.3, 125.3, 119.6, 76.2, 50.1, 48.5, 34.9, 34.8, 33.4, 29.7, 26.3.


(svn)-5-Cvclohexvl-4,.5-dihvdroxv-4-phenvl-1-Dentene (68)


Allyl bromide (0.9 mmol, 0.4 M THF) was added slowly to SmI2 (1.3 mmol, 0.1 M THF). The reaction was stirred at RT for 4 min and 65 (0.3 mmol, 1 mL THF) was added slowly.






63


After complete addition, the reaction was stirring for 10 min and the dark blue color of the SmI2 faded to green. The reaction was diluted with ethyl acetate and HCl (1 mL, 0.1 M) was added. The layers were allowed to separate and organic layer (1 pL) was injected in the GC. The organic layer was extracted with NaHCO3 (aq, sat) and NaCl (aq, Sat). The solution was dried over Na2SO4 filtered and reduced under vacuum. Column chromatography of the residue produced a white solid (0.059 g, 70%): Rf = 0.44 (CH2C12); 1H NMR (CDCI3) 7.4-7.2 (m, 5 H), 5.5-5.3 (m, 1 H), 5.2-5.1 (m, 1 H), 3.6 (d, J = 8 Hz, 1 H), 2.9-2.2 (m, 2 H), 2.3 (broad s, 2 H), 1.7-0.9 (m, 11 H); 13C NMR (CDCI3) 5 143.6, 133.5, 128.2, 126.6, 125.3, 120.0, 80.8, 78.7, 76.9, 45.6, 39.2, 31.9, 29.8, 26.6, 26.2, 25.6, 25.7; IR (KBr) 3475, 2921, 1446, 1266 cm-1.

Anal. Calcd. for C17H2402: C, 78.42%, H, 9.29%. Found: C, 78.27%; H, 9.29%.


(syn) -4,5-Dihvdroxy-4-Dhenyl-l-dodecene (71)


Allyl bromide (0.9 mmol, 0.4 M THF) was added slowly to SmI2 (1.3 mmol, 0.1 M THF). The reaction was stirred at RT for 4 min and 72 (0.3 mmol, 1 mL THF) was added slowly. After stirring for 10 min, the dark blue color of the SmI2 faded to green. The reaction was diluted with ethyl acetate and HCl (1 mL, 0.1 M) was added. The layers were allowed to separate and organic layer (1 RL) was injected in the GC. The organic layer was extracted with NaHCO3 (aq, sat) and NaCl (aq, Sat). The solution was dried over Na2SO4 filtered






64


and reduced under vacuum. Column chromatography of residue produced a clear oil: 1H NMR (CDCI3) 8 7.4-7.2 (m, 5 H) 5.65.4 (m, 1 H) 5.3-5.1 (m, 2 H) 3.7 (t, J = 7 Hz, 1 H), 2.8 (d, J = 7.5 Hz, 2 H), 1.4-1.1 (m, 12 H), 0.9 (t, J = 7 Hz, 3 H); 13C NMR (CDCI3) 8 142.9, 128.3, 128.0, 126.8, 126.5, 125.7, 79.17, 78.2, 45.9, 39.9, 29.3, 26.2, 22.7, 16.5, 14.5.


(Z)-4-Dhenvl-4-dodecene (75Z)


To a suspension of the ylide salt 73 (10.6 mmol in 10 mL THF) was added n-BuLi (3.2 mL, 2.5 M in hexanes) at 0C. The resulting red solution was stirred for 1 h, and butyrophenone (5.3 mmol) was added dropwise. After complete addition, the reaction was warmed to RT and stirred overnight. The

reaction was diluted with 40 mL of 1:1 ether-hexanes then filtered. The filtrate was washed with water, NaCl (sat, aq), dried with Na2SO4, and concentrated in vacuum to an oily white solid. The oily solid was dissolved in hexanes then filtered. The hexanes of the filtrate were removed in vacuum to yield a mixture of the E and Z isomers in a 4 : 1 ratio as determined by GC and 1H NMR (See Figure 5 in Appendix). After column chromatography, 75Z was isolated. IH NMR

(CDCI3) 8 7.4-7.1 (m, 5 H), 5.4 (t, J = 7 Hz, 1 H), 2.3 (t, J = 7.5 Hz, 2 H), 1.9 (q, J = 7.5 Hz, 2 H), 1.4-1.1 (m, 10 H), 0.9-0.8 (m, 6 H); 13C NMR (CDCl3) 8 140.7, 128.4, 127.8, 127.5, 126.1, 41.4, 31.7, 30.1, 29.7, 28.8, 28.7, 22.5, 21.2, 13.9, 13.5; IR (neat) 2926, 1690, 1599, 1463, 1377, 1119, 700 cm-1.






65


Anal. Calcd. for C17H26: C, 88.62%, H, 11.38%. Found: C, 88.34%; H, 11.25%.


4.5-Dihvdroxy-4-henvldodecane (76)


4-Phenyl-4-dodecene (0.87 mmol, 4:1 mixture of isomers) and silver acetate (1.73 mmol) were added to acetic acid (4 mL) and stirred rapidly. Iodide (0.87 mmol in 4.5 mL acetic acid) was added to the reaction mixture dropwise over 1 h, then stirred for 15 min. Water (8 mmol) was added and the reaction was stirred 18 h then heated to 700C for 2 h. The reaction mixture was concentrated under vacuum, dissolved in ether and filtered. The filtrate was concentrated under vacuum then treated with K2CO3 (anhy) in methanol (1 mL) for 30 min. This mixture was dissolved in ethyl acetate, washed with water and NaCl (sat, aq), dried over Na2SO4, and filtered. The solvent was removed under reduced pressure. Column chromatography yielded 76 (0.10 g, 45%) as a 4 : 1 mixture of threo and erythro diastereomers as determined by GC and 1H NMR. The title compound was also produced by hydrogenation of 71 with H2/Pd on carbon. The results of the two procedures were compared by GC and 1H NMR (See Figures 89 in Appendix). 1H NMR (CDCI3) 6 7.5-7.2 (m, 5 H), 3.8-3.2 (m, 1 H), 2.6 (s, 1 H), 2.5 (s, 1 H), 2.0-1.7 (m, 5 H), 1.3-1.1 (m, 9 H), 0.8 (m, 6 H); 13C NMR (CDCI3) 8 144.2, 142.9, 128.2, 128.0, 126.5, 126.0, 125.7, 78.3, 78.2, 41.3, 31.8, 31.7, 31.3, 29.3, 29.1, 26.3, 22.6, 22.5, 16.5, 14.5, 14.1.






66


Anal. Calcd. for 017H2602: C, 77.22%, H, 10.67%. Found: C, 77.38%; H, 11.01%.


Tetrahydro-2H-pyvran-2-carboxvlic acid (90, n=2)


To tetrahydro-2H-pyran-2-methanol (10 g, 0.086 mole) in acetone (170 mL) at 00C was added the Jones reagent (made from 27 g chromium trioxide, 23 mL H2SO4 and 75 mL H20) in portions over 1 h until the solution remained red. The

reaction was quenched with isopropanol, and the acetone was removed under reduced pressure. The remaining slush was extracted with ethyl acetate and filtered. The filtrate was washed with water and brine then dried over Na2SO4. This solution was filtered and the solvents were removed under vacuum to give, after column chromatography, 90 (n = 2) as clear colorless oil (7.8 g, 68%): Rf 0.04 (35% THF/hexane); 1H NMR (CDC13) 8 9.6 (broad s, 1 H), 4.1 (m, 2 H), 3.5 (m, 1 H), 2.1 (m, 1 H), 1.9 (m, 1 H), 1.6 (m, 4 H); 13C NMR (CDC13) 8 174.8, 74.4, 67.1, 27.5, 24.0, 21.7; IR (neat) 3141, 2943, 1742, 1442, 1209, 1097, 1052, 906 cm-1.

Anal. Calcd. for CO1H1003: C, 55.37; H, 7.74. Found: C, 55.29; H, 8.14.


Phenvl tetrahvdro-2H-nvran-2-vl ketone (95)


To a solution of phenylmagnesium bromide (70 mmol) in THF (50 mL) at 00C, was added carboxylic acid (20 mmol, in 25 mL of THF) rapidly with stirring. After 30 min at 0C, the reaction was warmed to RT and quenched by pouring the






67


reaction into an ice/HCl mixture. The resulting solution was extracted with ethyl ether. The organic layer was separated and washed with NH4C1 (aq, sat) and NaCl (aq, sat). The

solution was dried with Na2SO4 and reduced under vacuum. Column chromatography produced 2-[diphenylhydroxymethyl]tetrahydropyran and 95 as a clear colorless oil: Rf 0.52 (35% THF/hexane); 1H NMR (CDC13) 8 7.97 (dd, J = 2, 8 Hz, 2 H), 7.53 (m, 1 H), 7.44 (m, 2 H), 4.71 (dd, J = 2, 8 Hz, 1 H), 4.14 (split d, 1 H), 3.62 (complex t, 1 H), 1.93 (m, 2 H), 1.75-1.54 (m, 4 H); 13C NMR (CDC13) 8 198.3, 135.2, 133.1, 128.8, 128.4, 79.8, 68.6, 28.8, 25.5, 23.1; IR (neat) 2940, 2850, 1692, 1597, 1448, 1227, 1091, 971, 695 cm-1.

Anal. Calcd. for C12H1402: C, 75.76; H, 7.42. Found: C, 76.12; H, 7.55.


2- [Diphenylhydvroxymethy 1 tetrahydropyran (101)


Column chromatography of the above procedure produced 101 as a white solid: 1H NMR (CDC13) 8 7.5-7.1 (m, 10 H), 4.05 (m, 1 H), 3.85 (m, 1 H), 3.41 (m, 1 H), 3.18 (s, 1 H) 1.7-0.9 (m, 6 H); 13C NMR (CDC13) 8 146.6, 144.0, 128.0, 126.9, 126.7, 126.6, 125.9, 80.3, 79.3, 68.8, 25.9, 25.0, 23.4; IR (KBr) 3494, 2848, 2957, 1598, 1448, 1333, 1184, 1065, 874, 698 cm-1.

Anal. Calcd. for C18H2002: C, 80.56; H, 7.51. Found: C, 80.52; H, 7.56.






68


General procedure for alkylations using organolithium



To a well stirred solution of the carboxylic acid (4.1 mmol) in THF (10 mL) at 0C, was added the organolithium (10.25 mmol) dropwise over 1/2 h. This solution became very thick as the insoluble carboxylate salt was formed, and then returned clear as the reaction proceeded. After complete addition, the reaction was allowed to warm to RT, and was stirred for 24 h. The reaction was quenched by pouring slowly into a vigorously stirred solution of ice and dilute HCI. The resulting solution was extracted with ethyl ether (5 x 15 mL). The organic layers were combined and extracted with NaHC03 (aq, sat) and brine (aq, sat), then dried with Na2SO4. The solution was filtered and reduced under vacuum. The resulting oil was purified by column chromatography. The NaHCO3 extracts can be acidified to recover any unreacted starting materials.


Phenvl tetrahvdrofuran-2-vl ketone (92)


To a well stirred solution of the tetrahydro-2H-furan-2carboxylic acid (4.1 mmol) in THF (3 mL) at 0C, was added the phenyllithium (9 mmol), dropwise over 1/2 h. After

complete addition the reaction was allowed to warm to RT, and was stirred for 24 h. The reaction was quenched by pouring slowly into a vigorously stirred solution of ice and dilute HCI. The resulting solution was extracted with ethyl ether (5 x 10 mL). The organic layers were combined and washed






69


with NaHCO3 (aq, sat) and brine (aq, sat), then dried with Na2SO4. The solution was filtered and reduced under vacuum. The resulting oil was purified by column chromatography to produce a colorless oil: Rf = 0.17 (20% Et20/Hex); 1H NMR (CDC13) 8 8.0 (m, 2 H), 7.6-7.4 (m, 3 H), 5.25 (dd, J = 6, 8 Hz, 1 H), 4.1-3.9 (m, 2 H), 2.35-2.25 (m, 1H), 2.2-2.05 (m, 1 H), 2.02-1.9 (m, 2 H); 13C NMR (CDC13) 8 198.8, 134.9, 133.2, 128.6, 128.5, 79.9, 69.3, 29.2, 25.6.

Anal. Calcd. for C11H1202: C, 74.94; H, 6.87. Found: C, 74.69; H, 6.92.


1-(Tetrahydro-2'H-pyran-2'-yl)-1-Dentanone (94)


To a well stirred solution of the tetrahydro-2H-pyran-2carboxylic acid (3.3 mmol) in THF (10 mL) at 00oC, was added the n-butyllithium (9.4 mmol) dropwise over 1/2 h. After complete addition the reaction was allowed to warm to RT, and was stirred for 24 h. The reaction was quenched by pouring slowly into a vigorously stirred solution of ice and dilute HC1. The resulting solution was extracted with ethyl ether (5 x 10 mL). The organic layers were combined and extracted with NaHCO3 (aq, sat) and NaCl (aq, sat), then dried with Na2SO4. The solution was filtered and reduced under vacuum. The resulting oil was purified by column chromatography to produce a colorless oil: Rf = 0.44 (35% THF/hexane); 1H NMR (CDC13) 8 4.05 (m, 1 H), 3.78 (dd, J = 2.3, 11 Hz, 1 H), 3.46 (m, 1 H), 2.54 (t, J = 7.5 Hz, 2 H) 1.88 (m, 2 H), 1.62-1.23






70


(m, 8 H), 0.91 (t, J = 8 Hz, 3 H); 13C NMR (CDC13) 8 211.1, 82.8, 68.2, 37.5, 28.2, 25.5, 25.1, 23.1, 22.3, 13.8.

Anal. Calcd. for C10H1802: C, 70.55; H, 10.65. Found: C, 70.22; H, 10.84.


Cyclohexane tetrahvdroDvran-2-vl ketone (96)


To a well stirred solution of the tetrahydro-2H-furan-2carboxylic acid (3.8 mmol) in THF (10 mL) at 00C, was added the cyclohexyllithium (8.2 mmol) dropwise over 1/2 hour. After complete addition the reaction was allowed to warm to RT, and was stirred for 24 h. The reaction was quenched by pouring slowly into a vigorously stirred solution of ice and dilute HC1. The resulting solution was extracted with ethyl ether (5 x 10 mL). The organic layers were combined and extracted with NaHCO3 (aq, sat) and brine (aq, sat), then dried with Na2SO4. The solution was filtered and reduced under vacuum. The resulting oil was purified by column chromatography to produce a colorless oil: 1H NMR (CDC13) 6

4.1-4.0 (m, 1 H), 3.9-3.7 (m, 1 H), 3.5-3.4 (m, 1 H), 2.5 (doublet of triplet, J = 2, 7.5 Hz, 1 H), 2.0-1.1 (m, 16 H); 13C NMR (CDCl3) 8 210.7, 82.5, 67.9, 37.2, 27.9, 25.2, 24.9, 22.9, 22.0, 13.5.

Anal. Calcd. for C12H2002: C, 73.43; H, 10.27. Found: C, 73.70; H, 10.67.






71


2-Cyclohexyl-- (tetrahydro-2'H-Dyran-2'-vl)ethan-l-one (97)


To a well stirred solution of the tetrahydro-2H-pyran-2carboxylic acid (4.2 mmol) in THF (15 mL) at 00C, was added the organolithium (8.8 mmol) dropwise over 0.5 h. After

complete addition the reaction was allowed to warm to RT, and was stirred for 24 h. The reaction was quenched by pouring slowly into a vigorously stirred solution of ice and dilute HC1. The resulting solution was extracted with ethyl ether (5 x 10 mL). The organic layers were combined and extracted with NaHCO3 (aq, sat) and brine (aq, sat), then dried with Na2SO4. The solution was filtered and reduced under vacuum. The resulting oil was purified by column chromatography to produce a colorless oil: Rf = 0.44 (5% MeOH/CHC13); 1H NMR (CDC13) 8 4.0 (m, 1 H), 3.7 (dd, J = 2, 11 Hz, 1 H), 3.4 (m, 1 H), 2.3 (d, J = 7 Hz, 2 H), 1.9 1.7 (m, 3 H), 1.65 1.0 (m, 12 H), 0.95 0.75 (m, 2 H); 13C NMR (CDCl3) 8 210.4, 83.0, 68.2, 45.3, 33.2, 32.9, 28.0, 26.2, 26.0, 25.4, 23.1;
Anal. Calcd for C13H2202: C, 74.24; H, 10.55. Found: C, 74.28; H, 10.51.


2-Phenyl-l-(tetrahydro-2'H-pyran-2'-vl)-l-ethanone (99)


To a well stirred solution of the tetrahydro-2H-pyran-2carboxylic acid (2 mmol) in THF (6 mL) at 0OC, was added the organolithium reagent (5 mmol) dropwise over 1/2 h. After complete addition the reaction was allowed to warm to RT, and was stirred for 24 h. The reaction was quenched by pouring






72


slowly into a vigorously stirred solution of ice and dilute HCI. The resulting solution was extracted with ethyl ether (5 10 mL). The organic layers were combined and extracted with NaHC03 (aq, sat) and brine (aq, sat), then dried with Na2SO4. The solution was filtered and reduced under vacuum. The resulting oil was purified by column chromatography to produce a colorless oil: Rf = 0.37 (20% Et20/hex.); 1H NMR (CDCl3) 8 7.4-7.2 (m, 5 H), 4.08 (m, 1 H), 3.87 (d, J = 5 Hz, 2 H), 3.8 (m, 1 H), 3.48 (m, 1 H), 1.9-1.8 (m, 2 H), 1.7-1.3 (m, 4 H); 13C NMR (CDCI3) 8 208.1, 134.1, 129.8, 128.4, 126.8, 82.2, 68.3, 44.8, 28.2, 25.6, 23.0; IR (neat) 2939, 2852, 1718, 1090 cm-1.

Anal. Calcd. for C13H1602: C, 76.44; H, 7.90. Found: C, 76.21; H, 7.90.


l-Phenyl(tetrahvdro-2 'H-Dvran-2'-vl)methanol (103)


A mixture of 95 (0.83 mmol), nBu3SnH (0.91 mmol), and AIBN (0.25 mmol) in 8.3 mL of dry benzene was degassed with argon, then refluxed overnight. The solvent was removed under vacuum. Column chromatography yielded the alcohol 103 (0.15 g, 92.5%) as a 1:1 mixture of diastereomers: IH NMR (CDCI3) 8 7.4-7.2 (m, 5 H), 4.8 (t, J = 3.5 Hz, 0.5 H), 4.4 (dd, J = 2.5, 8 Hz, 0.5 H) 4.1-4.0 (m, 1 H), 3.5-3.3 (m, 2 H), 1.8-1.2 (m, 7 H); 13C NMR (CDCI3) 8 140.38, 140.36, 128.23, 128.04, 127.99, 127.91, 127.27, 126.42, 81.99, 81.18, 77.77, 75.70, 68.86, 68.49, 27.47, 25.99, 25.84, 24.17, 22.95, 22.87; IR (neat) 3443, 2939, 2854, 1451, 1204, 1089,






73


1046, 909 cm-1; 1H NMR is identical to lit. values.39 cas [110615-39-9), [110615-38-8]


Typical procedure for rina onenina with SmI

An a-ketotetrahydropyran (1 eq) in a small amount of THF was added slowly to a degassed solution of samarium diiodide (2.5 eq, 0.1 M in THF) and HMPA (5 eq) which was stirred for 15 min. The reaction was then quenched with water and stirred for 10 min. Dilute HC1 was added and the reaction was stirred for 30 min. The resulting mixture was extracted with ethyl acetate. The organic layer was washed with water several times to remove HMPA, then washed with NaHCO3 (aq, sat) and NaCl (aq, sat) and dried over Na2SO4. After

evaporation of the solvents, the product was purified by flash column chromatography.


Typical procedure for ring opening with addition of electroohile

An a-ketotetrahydropyran (1 eq) in a small amount of THF was added slowly to a degassed solution of samarium diiodide (2.5 eq in 0.1 M in THF) and HMPA (5 eq), then stirred for 20 min. The reaction was then quenched with an electrophile (4 eq) and stirred for 2 to 12 h, with monitoring by TLC. Water was added to the reaction followed by addition of dilute HCl. The reaction was then stirred for 30 min. The resulting mixture was extracted with ethyl acetate. The organic layer was washed with water several times to remove HMPA, then






74


washed with NaHCO3 (aq, sat) and NaCl (aq, sat) and dried over Na2SO4. After evaporation of the solvents, the product was purified by flash column chromatography. 10-Hydroxydecan-5-one (104)


A solution of 1-(tetrahydro-2'H-pyran-2'-yl)-l-pentanone (1.32 mmol in 1 mL THF) was added slowly to a degassed solution of samarium diiodide (3.3 mmol, 0.1 M in THF) and HMPA (6.6 mmol). The solution was stirred for 15 min at RT. The reaction was then quenched with water and stirred for 10 min. Dilute HCI was added and the reaction was stirred for 30 min. The resulting mixture was extracted with ethyl acetate. The combined organic layers were washed with water several times to remove HMPA. The organic layer was then washed with NaHCO3 (aq, sat) and NaCl (aq, sat) and dried over Na2SO4. After evaporation of the solvents, the product was purified by flash column chromatography to produce 104 (93%): Rf = 0.26 (35% THF/hexane); 1H NMR (CDCI3) 8 3.58 (t, J = 6 Hz, 2 H), 2.34 (q, J = 7.5, 4 H), 1.8 (broad s, 1 H), 1.4-1.6 (m, 6 H), 1.15-1.35 (m, 4 H), 0.80 (t, J = 7.3, 3 H); 13C NMR (CDC13) 8 211.6, 62.6, 42.6, 32.4, 26.0, 25.3, 23.4, 22.3, 13.8; IR (neat) 3398, 2936, 1710, 1454, 1054, 700 cm-1.

Anal. Calcd. for ClOH2002: C, 69.72; H, 11.70. Found: C, 69.45; H, 11.72.






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6-Hvdroxv-1-Dhenylhexan-1-one (105)


Phenyl tetrahydro-2H-pyran-2-yl ketone (1.1 mmol) was added slowly to a degassed solution of samarium diiodide (2.82 mmol, 0.1 M in THF) and HMPA (5.6 mmol) at 00C. The solution was stirred for 15 min at RT. The reaction was then quenched with water and stirred for 10 min. Dilute HC1 was added and the reaction was stirred for 30 min. The resulting mixture was extracted with ethyl acetate. The organic layers were washed with water several times to remove HMPA. The

organic layer was then washed with NaHCO3 (aq, sat) and NaCl (aq, sat) and dried over Na2SO4. After evaporation of the solvents, the product was purified by flash column chromatography to produce 105 as an oil (53%): Rf = 0.17 (35% THF/hexane); 1H NMR (CDC13) 8 7.95 (dd, J = 2, 8 Hz, 2 H), 7.55 (m, 1 H), 7.45 (m, 2 H), 3.66 (t, J = 7 Hz, 2 H), 2.98 (t, J = 7 Hz, 2 H), 1.93 (broad s, 1 H), 1.77 (m, 2 H), 1.62 (m, 2 H), 1.46 (m, 2 H); 13C NMR (CDCl3) 8 200.4, 136.9, 132.9, 128.5, 128.0, 62.5, 38.4, 32.4, 25.4, 23.8; IR (neat) 3405, 2837, 1681, 1598, 1449, 1369, 1221, 1052, 691 cm-1; cas [17851-49-9].

Anal. Calcd: C, 74.96; H, 8.39. Found: C, 74.82; H,

8.59.


1-Cyclohexyl-6-hydroxy-1-hexanone (114)


Cyclohexane tetrahydropyran-2-yl ketone (0.66 mmol) in a small amount of THF was added slowly to a degassed solution






76


of samarium diiodide (1.7 mmol, 0.1 M in THF) and HMPA (3.3 mmol). The solution was stirred for 15 min at room temperature. The reaction was then quenched with water and stirred for 10 min. Dilute HC1 was added and the reaction was stirred for 30 min. The resulting mixture was extracted with ethyl acetate. The organic layers were washed with water several times to remove HMPA. The organic layer was then washed with NaHCO3 (aq, sat) and NaCl (aq, sat) and dried over Na2SO4. After evaporation of the solvents, the product was purified by flash column chromatography to produce 114 as an oil (81%): Rf = 0.22 (35% THF/hexane); 1H NMR (CDC13) 8 3.6 (t, J = 6.4 Hz, 2 H), 2.4 (pent, J = 7.5 Hz, 3 H), 2.2 (broad s, 1 H), 1.6-1.1 (m, 15 H), 0.9-0.7 (m, 2 H); 13C NMR (CDC13) 6 211.5, 62.4, 42.5, 40.3, 37.3, 33.1, 32.4, 31.2, 26.5, 26.2, 25.3, 23.5; IR (neat) 3405, 2923, 1709, 1449, 1374, 1054 cm-1.

Anal. Calcd. for C12H2202: C, 72.68; H, 11.19. Found: C, 72.93; H, 11.41.


7-Hvdroxy-1-Dhenvl-2-heptanone (115)


A solution of 2-phenyl-1-(tetrahydro-2'H-pyran-2'-yl)-1ethanone (0.52 mmol, 0.5 mL THF) was added slowly to a degassed solution of samarium diiodide (1.3 mmol, 0.1 M in THF) and HMPA (2.6 mmol). The solution was stirred for 15 min at room temperature. The reaction was then quenched with water and stirred for 10 min. Dilute HCl was added and the reaction was stirred for 30 min. The resulting mixture was






77


extracted with ethyl acetate. The combined organic layers were washed with water several times to remove HMPA. The organic layer was then washed with NaHCO3 (aq, sat) and NaCl (aq, sat) and dried over Na2SO4. After evaporation of the solvents, the product was purified by flash column

chromatography to produce 115 as an oil (72%): Rf = 0.26 (35% THF/hexanes); 1H NMR (CDC13) 6 7.4-7.2 (m, 5 H), 3.7 (s, 2 H), 3.6 (t, J = 6.2 Hz, 2 H), 2.5 (t, J = 7.3 Hz, 2 H), 1.55 (m, 5 H), 1.3 (m, 2 H); 13C NMR (CDC13) 6 208.6, 134.2, 129.4, 128.7, 127.0, 62.5, 50.2, 41.8, 32.3, 25.1, 23.3

Anal Calcd. for C13H1802: C, 75.57; H, 8.79. Found: C, 75.25; H, 8.93.


l-Cvclohexvl-7-hvdroxv-2-heptanone (116)


A solution of 2-cyclohexyl-l-(tetrahydro-2'H-pyran-2'yl)ethan-1-one (0.76 mmol, 1 mL THF) was added to a degassed solution of samarium diiodide (1.86 mmol, 0.1 M in THF) and HMPA (3.8 mmol). The solution was stirred for 15 min at RT. The reaction was then quenched with water and stirred for 10 min. Dilute HC1 was added and the reaction was stirred for 30 min. The resulting mixture was extracted with ethyl acetate. The organic layer was washed with water several times to remove HMPA. The organic layer was then washed with NaHCO3 (aq, sat) and NaCl (aq, sat) and dried over Na2SO4. After evaporation of the solvents, the product was purified by flash column chromatography to produce 116 as an oil (45%): Rf = 0.26 (35% THF/Hexanes); 1H NMR (CDC13) 8 3.6 (t,






78


J = 6.6 Hz, 2 H), 2.3 (t, J = 7.4 Hz, 2 H), 2.2 (d, J = 7 Hz, 2 H), 1.9 (broad s, 1 H), 1.8 (m, 1 H), 1.7-1.5 (m, 8 H), 1.4-1.0 (m, 6 H), 0.95-0.8 (m, 2 H); 13C NMR (CDC13) 8 211.2, 62.5, 50.5, 43.3, 33.9, 33.2, 32.4, 26.1, 26.0, 25.3, 23.3; IR (neat) 3406, 2923, 1710, 1375, 1054 cm-1.

Anal. Calcd. for C13H2402: C, 73.54; H, 11.39. Found: C, 73.43; H, 11.57.


Addition product of dihydrocarvone and 94


A solution of 1-(Tetrahydro-2'H-pyran-2'-yl)-1-pentanone (0.5 mmol, 0.5 mL THF) was added slowly to a degassed solution of samarium diiodide (2 mmol, 0.1 M in THF) and HMPA (4 mmol), then stirred for 20 min. The reaction was then quenched with dihydrocarvone (4 eq) and stirred for 8 h. Water was added to the reaction followed by addition of dilute K2CO3 and the reaction was stirred for 30 min. The resulting mixture was extracted with ethyl acetate. The

organic layer was washed with NaHCO3 (aq, sat) and NaCl (aq, sat) and dried over Na2SO4. After evaporation of the

solvents, the product was purified by flash column
chromatography to produce an oil (14%): 1H NMR 8 (CDC13) 4.62 (m, 2 H), 3.56 (t, J = 7.5 Hz, 2 H), 2.33 (m, 2 H), 2.18 (in, 1 H), 1.95 (s, 1 H), 1.65 (s, 3 H), 1.5-1.1 (m, 17 H), 0.95 (d, J = 7.5 Hz, 3 H), 0.83 (t, J = 7.5 Hz, 3 H)






79


Addition Droduct of cyclohenanone and 94

a-Ketotetrahydropyran 94 (1 eq) was added slowly with the help of a little THF to a degassed solution of samarium diiodide (2.5 eq., 0.1 M in THF), then stirred for 20 min. The reaction was then quenched with cyclohexane (4 eq) and stirred for 2 h. Water was added to the reaction followed by addition of dilute K2C03 and the reaction was stirred for 30 min. The resulting mixture was extracted with ethyl acetate. The organic layer was washed with NaHCO3 (aq, sat) and NaCI (aq, sat) and dried over Na2SO4. After evaporation of the solvents, the product was purified by flash column

chromatography to produce an oil (33%): 1H NMR 8 (CDC13) 3.56 (m, 2 H), 3.0 (broad s, 1 H), 2.55 (dd, J = 6, 12 Hz, 1 H), 2.43 (m, 2 H), 1.7-1.1 (mn, 24 H), 0.84 (t, J = 12 Hz, 3 H); 13C NNR (CDC13) 6 200.1, 72.7, 62.4, 59.3, 47.2, 37.4, 34.8, 32.0, 27.0, 25.7, 24.8, 24.5, 22.2, 21.9, 21.6, 13.9. 2-Benzyl-6-hydroxy-1-Phenyl-l-hexanone (120)


Phenyl tetrahydro-2H-pyran-2-yl ketone (1.1 mmol, 1 mL THF) was added slowly to a degassed solution of samarium diiodide (2.7 mmol, 0.1 M in THF) and HMPA (5.4 mmol) which was stirred for 30 min. The reaction was then quenched with benzyl bromide (4.4 mmol) and stirred for 2 h, monitoring by TLC. Water was added to the reaction followed by addition of dilute HC1 and the reaction was stirred for 30 min. The

resulting mixture was extracted with ethyl acetate. The






80


organic layer was washed with water several times to remove HMPA, then washed with NaHCO3 (aq, sat) and NaCI (aq, sat) and dried over Na2SO4. After evaporation of the solvents, the product was purified by flash column chromatography: Rf = 0.48 (8% MeOH/CHC13); 1H NMR (CDC13) 8 7.85 (m, 2 H), 7.6-7.1 (m, 8 H), 3.7 (m, 1 H), 3.55 (t, J = 6 Hz, 2 H), 3.09 (dd, J = 6, 8 Hz, 1 H), 2.76 (dd, J = 7 Hz, 1H), 1.9-1.2 (m, 7 H); 13C NMR (CDCl3) 8 203.9, 139.8, 137.4, 132.9, 129.0, 128.6, 128.4, 128.1, 126.2, 62.5, 48.3, 38.4, 32.7, 31.9, 23.6; IR (neat) 3387, 2932, 1677, 1443, 1230, 1073 cm-1.

Anal. Calcd. for C19H2202: C, 80.82; H, 7.85. Found: C, 80.62; H, 7.99.


2-AlylV-6-hyvdroxy-1-Dhenyl-1-hexanone (121)


Phenyl tetrahydro-2H-pyran-2-yl ketone (1.1 mmol) in a small amount of THF, was added slowly to a degassed solution of samarium diiodide (2.7 mmol, 0.1 M in THF) and HMPA (5.5 mmol), then stirred for 20 min. The reaction was then

quenched with allyl bromide (4.4 mmol) and stirred for 12 h. Water was added to the reaction followed by addition of dilute HC1 and the reaction was stirred for 30 min. The

resulting mixture was extracted with ethyl acetate. The

organic layer was washed with water several times to remove

HMPA, then washed with NaHCO3 (aq, sat) and NaCl (aq, sat) and dried over Na2SO4. After evaporation of the solvents, the product was purified by flash column chromatography: Rf = 0.26 (35% THF/hexanes); 1H NMR (CDCl3) 8 7.95 (m, 2 H), 7.60-






81


7.40 (m, 3 H), 5.81-5.65 (m, 1 H), 5.05-4.93 (m, 2 H), 3.57 (t, J = 6 Hz, 2 H), 3.53 (m, 1 H), 2.57-2.45 (m, 1 H), 2.322.20 (m, 1 H), 2.15 (broad s, 1 H), 1.88-1.75 (m, 1 H), 1.631.48 (m, 3 H), 1.40-1.28 (m, 2 H); 13C NMR (CDCI3) 8 203.8, 137.2, 135.6, 133.0, 128.6, 128.2, 116.7, 62.4, 45.8, 36.5, 32.5, 31.5, 23.6; IR (neat) 3412, 2936, 1679, 1447, 1234 cm-1.

Anal. Calcd. for C19H2002: C, 77.55; H, 8.68. Found: C, 77.40; H, 8.67.


2- ((E)-2 '-Butenyl)-6-hydroxy-l-phenvl-l-hexanone (122)


Phenyl tetrahydro-2H-pyran-2-yl ketone (1 mmol) was added slowly with the help of a little THF to a degassed solution of samarium diiodide (2.5 mmol, 0.1 M in THF) and HMPA (5 mmol) which was stirred for 20 min. The reaction was then quenched with crotyl bromide (4 mmol) and stirred for 4 h, monitoring by TLC. Water was added to the reaction followed by addition of dilute HCl and the reaction was stirred for 30 min. The resulting mixture was extracted with ethyl acetate. The organic layer was washed with water several times to remove HMPA, then washed with NaHCO3 (aq, sat) and NaCl (aq, sat) and dried over Na2SO4. After

evaporation of the solvents, the product was purified by flash column chromatography to yield 122 as a 3 to 1 mixture of cis-trans isomers (61%). Further chromatography provided

the E isomer: Rf = 0.52 (10% MeOH/CHCI3); IH NMR (CDCI3) 8 7.9 (m, 2 H), 7.5 (m, 3 H), 5.5-5.3 (m, 2 H), 3.6 (t, J = 6.8 Hz, 2 H), 3.5 (m, 1 H), 2.5-2.1 (m, 2 H), 1.9-1.7 (m, 2 H), 1.65-






82


1.45 (m, 6 H), 1.4-1.25 (m, 2 H); 13C NMR (CDC13) 8 203.9, 137.5, 132.7, 128.6, 128.2, 128.0, 62.5, 46.5, 46.3, 35.4, 32.8, 31.3, 23.6, 17.7.

Anal. Calcd. for C16H2202: C, 78.01; H, 9.00. Found: C, 77.83; H, 9.10.


6-Trimethylsiloxy-1-phenyl-1-hexanone (124)


Phenyl tetrahydro-2H-pyran-2-yl ketone (0.4 mmol, 1 mL THF) was added dropwise to a degassed solution of samarium diiodide (1.1 mmol, 0.1 M in THF). HMPA (4 mmol) was added and the reaction was stirred for 1 h. The reaction was then quenched with TMSCl (1.6 mmol) and stirred for 3 h, then heated to 550C for 12 h. The reaction was cooled and water was added to the reaction followed by addition of K2CO3 (aq, sat) and the reaction was stirred for 30 min. The resulting mixture was extracted with ethyl acetate. The organic layer was washed with water several times to remove HMPA, then

washed with NaHCO3 (aq, sat) and NaCl (aq, sat) and dried over Na2SO4. After evaporation of the solvents, the product was purified by flash column chromatography to produce 124 (53.7%): 1H NMR (CDC13), no TMS added 6 7.86 (m, 2 H), 7.57.3 (m, 3 H), 3.48 (t, J = 6 Hz, 2 H), 2.87 (t, J = 7.5 Hz, 2 H), 1.7-1.3 (m, 6 H), 0.0 (s, 9 H); 13C NMR (CDC13), no TMS added, 8 200.8, 133.4, 133.3, 129.0, 128.5, 62.9, 39.0, 33.0, 36.2, 24.7, 0.0.






83


Methyl 2,3-isoprovpylidene-0-D-ribofuranoside (139)


D-ribose (25 g) was dissolved in acetone (95 mL) and methanol (95 mL) and refluxed 19 h. The reaction mixture was cooled with an ice bath and neutralized with pyridine (3 mL). The reaction was diluted with water (200 mL) and extracted with ether (200 mL). The organic layer was washed with CuSO4, dried over Na2SO4 and the solvent was removed under reduced pressure. The crude product was distilled to give the known compound41 139 (15.2 g, 50.3%): bp 1200C (12 mm Hg); 1H NMR (CDC13) 8 4.98 (s, 1 H), 4.83 (d, J = 6 Hz, 1 H), 4.59 (d, J = 6 Hz, 1 H), 4.43 (m, 1 H), 3.68 (m, 2 H), 3.43 (s, 3 H), 3.35 (m, 1 H), 1.49 (s, 3 H), 1.32 (s, 3 H).


Methyl 2,3-O-isooroyvlidene-0-D-ribo-pentodialdo-1,.4furanoside (140)

To oxalyl chloride (0.51 mL, 13 mL CH2Cl2) was added DMSO (0.84 mL in 2 mL CH2Cl2) dropwise, maintaining a temperature below -600C. Compound 139 (5 mL CH2C12) was then added dropwise and the reaction was stirred for 15 min at

-600C. Triethyl-amine (3.7 mL) was added and the reaction was allowed to warm to RT. The solution was poured into ether (40 mL) and water (15 mL). The ether layer was washed with water (15 mL), NaCl (aq, sat), and dried over Na2SO4. The solvent was removed under reduced pressure to yield the known compound41 140 (0.72g, 73%): 1H NMR (CDC13) 6 9.6 (s, 1 H), 5.1 (s, 1 H), 5.0 (d, J = 6 Hz, 1 H), 4.5 (d, J = 6 Hz, 1 H), 4.45 (s, 1 H), 3.5 (s, 3 H), 1.5 (s, 3 H), 1.3 (s, 3 H);






84


13C NMR (CDC13) 8 200.8, 112.7, 109.1, 89.5, 83.9, 80.7, 55.7, 26.2, 24.8.


Methyl 2.,3-O-Isooropylidene-5-Dhenvl-0-D-ribofuranoside (141)


To magnesium turnings (18.6 mmol) in ethyl ether (6 mL) was added bromobenzene (2 mL ether) dropwise, maintaining a gentle reflux. The resulting solution was cooled to 00C and 140 (3.7 mmol in 2 mL ether) was added dropwise. After

complete addition the reaction was warmed to RT and poured into a flask containing ice and NH4C1 (aq, sat). This

mixture was extracted with ether. The combined ether layers were washed with NH4Cl (aq, sat), NaCl (aq, Sat), dried over Na2SO4 and the solvent was removed under vacuum. Column chromatography of the crude material yielded 141 (0.83g, 83%) as a yellowish oil. See NMR spectra in Appendix.


Methyl 5-deoxvyphenylketo-2.3-O-isoproDvlidene-B-DriboDvranoside (142)


To oxalyl chloride (1.88 mL in 31 mL CH2Cl2) was added DMSO (3.12 mL in 12 mL CH2C12) dropwise, maintaining a temperature below -600C. After complete addition, 141 (6 mL CH2C12) was added dropwise and the reaction was stirred 15 min at -600C. Triethylamine (13 mL) was added and the reaction was allowed to warm to RT. The solution was poured into ether (120 mL) and water (40 mL). The ether layer was washed with water (45 mL), NaCl (30 mL, aq, sat), and dried over Na2so4. The solvent was removed under reduced pressure and






85


the crude oil was crystallized from methanol to afford 142 as

a white solid: (l.70g, 60%): mp 1240C; Rf = 0.62 (35% THF/Hex); [(a]23D +141.9 (c 0.160, CHC13) ; 1H NMR (CDC13) 6 8.0 (m, 2 H), 7.5 (m, 3 H), 5.5 (d, J = 6 Hz, 1 H), 5.3 (s, 1 H), 4.9 (s, 1 H), 4.6 (d, J = 6 Hz, 1 H), 2.9 (s, 3 H), 1.5 (s, 3 H), 1.3 (s, 3 H); 13C NMR (CDC13) 8 193, 135, 133, 129. 113, 109, 87, 85, 81, 56, 27, 25.
Anal. Calcd. for C15isH1805: C, 64.73; H, 6.52. Found: C, 64.72; H, 6.52.


1,2:3,4-Di-O-isopronylidene aalactopyranose (143)


To a suspension of CuSO4 (20 g, 128 mmol) and Dgalactose (9 g, 50 mmol) in acetone (200 mL) was added H2SO4 (1 mL), and stirred 24 h. The reaction was filtered, and the filtrate was neutralized with calcium hydroxide. The solvent was removed under vacuum and the crude oil was purified by column chromatography to yield the known compound 143 (4 g, 31%).45


1,2:3.4-Di-O-isoroDvylidene-l-Dhenyl aalactoDvranose (144)


To oxalyl chloride (0.73 mL in 10 mL CH2C12) was added DMSO (1.2 mL in 4 mL CH2Cl2) dropwise, maintaining a temperature below -600C. After complete addition, 143 (2 mL CH2C12) was added dropwise and the reaction was stirred 15 min at -600C. Triethylamine (5 mL) was added and the reaction was allowed to warm to RT. The solution was poured into ether (40 mL) and water (15 mL). The ether layer was washed






86


with water (45 mL), NaCl (aq, sat), and dried over Na2SO4. The solvent was removed under reduced pressure and the crude oil (1.05 g) was dissolved in 2 mL THF and added dropwise, at 000C, to phenylmagnesium bromide (5 mL, 0.8 M ethyl ether). The reaction was warmed to RT and poured onto ice and NH4Cl sol. This mixture was extracted with ether. The combined ether layers were washed with NH4C1 (aq, sat), NaCI (aq, Sat), dried over Na2SO4 and the solvent was removed under vacuum. Column chromatography of the crude material yielded 144 (0.6 g, 45%). See spectra in Appendix.


6-DeoxypDhenylketo-1, 2:3,4-di-O-isooronylidene aalactopyranose
(145)

To oxalyl chloride (0.37 mL in 9 mL CH2C12) was added DMSO (0.61 mL in 4 mL CH2C12) dropwise, maintaining a temperature below -600C. After complete addition, 144 (0.46 g, 1.44 mmol) in 2 mL CH2C12 was added dropwise and stirred 30 min at -600C. Triethylamine (13 mL) was added and the reaction was allowed to warm to RT. The solution was poured into ether (30 mL) and water (16 mL). The ether layer was washed with water (15 mL), NaCl (aq, sat), and dried over Na2SO4. The solvent was removed under reduced pressure to afford 145 as a white solid: 1H NMR (CDC13) 8 7.9 (m, 2 H), 7.4 (m, 3 H), 5.6 (d, J = 6 Hz, 1 H), 5.0 (s, 1 H), 4.6 (s, 1 H), 4.3 (d, J = 6 Hz, 1 H), 1.5 (s, 3 H), 1.3 (s, 3 H), 1.25 (s, 3 H), 1.15 (s, 3 H); 130 NMR (CDC13) 8 195.1, 135.7,






87


132.9, 128.8, 128.2, 109.7, 108.7, 72.1, 70.8, 70.4, 45.9, 25.9, 25.6, 24.6, 24.2.

Anal. Calcd. for C18H2206: C, 64.66; H, 6.63. Found: C, 64.60; H, 6.48.


1. 6-Anhvdro-2.3,4-tri-0-benzvl-B-D-alucoDvranose (147)


Corn starch was dried at 1000C for 24 h with stirring to accelerate the process. A 500 mL round bottom flask was filled with the dried corn starch (ca. 100 g) and a 600 curved glass connector was placed on top. A 1 L suction flask was attached to the connector and the suction flask was cooled with an ice bath. The suction flask was attached to a mild aspirator while the corn starch was heated evenly and consistently with a flame. After heating for 1-2 h, a tan oil had collected in the suction flask. This oil was

dissolved in acetone (40 mL) and the reduced under vacuum to remove water. After the water was removed. The brown syrup was dissolved in tetrahydrofuran (120 mL) and acetonitrile (60 mL) and added to a flask charged with NaH (6 eq., 0.37 mol) which had been previously washed with pentane. Benzyl bromide (6 eq., 0.37 mol) was added slowly and the reaction was refluxed for 12 h. The reaction was quenched with water and the layers were separated. The water layer was extracted with ethyl acetate. The combined organic layers were washed with NaHCO4 (aq, Sat) and NaCl (aq, sat), dried with Na2SO4, and reduced under vacuum. The crude product was purified by






88


column chromatography to produce the title compound (6 g).42,46 See NMR spectra in Appendix. Phenvl 2,3,4-tri-O-benzyl-l-thio-D-alucopvranoside (148)

To a solution of 1,6-Anhydro-2,3,4-tri-0-benzyl-0-Dglucopyranose (1.4 g, 3.3 mmol) and trimethyl(phenylthio)silane (0.87 g, 4.8 mmol, 13 mL CH2C12) at 00C was added TMSOTf (0.23 g, 1.0 mmol). The mixture was stirred at RT for 10 h, poured into NaHCO3, and extracted with EtOAc. The organic layer was washed with water and NaCl (aq, sat), dried with Na2SO4 and reduced under vacuum. The residue was

dissolved in THF/MeOH (1:1) containing K2CO3 and the solution was stirred for 30 min at room temperature. The mixture was diluted with EtOAc, washed with water and NaCl (aq, sat), dried with Na2SO4 and reduced under vacuum. The residue was purified by column chromatography to yield the known compound 148 as a oil.42


1-Deoxy-2,.3,4-tri-O-benzyl-D-alucopyranose (149)


Compound 148 (0.61g, 1.1 mmol), tributyltin hydride (0.31 g, 1.2 mmol) and AIBN (0.06 g, 0.3 mmol) was added to a flask containing benzene (4 mL). The solution was degassed with a stream of argon for 10 min. The reaction mixture was refluxed for 3 h. The reaction was cooled and reduced under vacuum. The crude product was crystallized from hexanes to produce the title compound. See NMR spectrum in Appendix.






89


1.,6-Di-deoxv-6-phenvl-2.3.4-tri-O-benzvl-D-alucoDvranose
(150)


To oxalyl chloride (0.18 mL in 4 mL CH2C12) was added DMSO ( 0.3 mL in 1 mL CH2C12) dropwise, maintaining a temperature below -600C. After complete addition, 149 in 1 mL CH2C12 was added dropwise and stirred 15 min at -600C. Triethylamine (0.6 mL) was added and the reaction was allowed to warm to RT. The solution was poured into ether (40 mL) and water (15 mL). The ether layer was washed with water (45 mL), NaCl (aq, sat), and dried over Na2SO4. The solvent was removed under reduced pressure and the crude oil (1.05 g) was dissolved in 2 mL THF and added dropwise, at 00C, to phenylmagnesium bromide (5 mL, 0.8 M ethyl ether). The

reaction was warmed to RT and poured onto ice and NH4C1 sol. This mixture was extracted with ether. The combined organic layers were washed with NH4Cl (aq, sat), NaCl (aq, Sat), dried over Na2SO4 and the solvent was removed under vacuum. The crude material was purified by column chromatography and oxidized in the next procedure before spectral analysis.


1. 6-Di-deoxv-6-phenvlketo-2,3.4-tri-O-benzvl-D-alucopvranose,



To oxalyl chloride (0.37 mL in 9 mL CH2C12) was added DMSO (0.61 mL in 4 mL CH2C12) dropwise, maintaining a temperature below -600C. After complete addition, 151 (0.46 g, 1.44 mmol) in 2 mL CH2C12 was added dropwise and stirred for 30 min at -600C. Triethylamine (13 mL) was added and the






90


reaction was allowed to warm to RT. The solution was poured into ether (30 mL) and water (16 mL). The ether layer was washed with water (15 mL), NaCI (aq, sat), and dried over Na2SO4. The solvent was removed under reduced pressure. The crude material was purified by column chromatography to afford 151 as a white solid: (1H NMR is displayed in Appendix); 13C NMR (CDCI3) 8 195,5, 138.5, 137.9, 137.6, 135.9, 133.6, 129.1, 128.5, 128.4, 128.3, 128.1, 127.9, 127.85, 127.8, 127.7, 127.5, 85.9, 79.3, 78.7, 77.9, 75.6, 75.1, 73.4, 68.5.


Procedure for rina openina of 151 with SmI,


Compound 151 (0.17 mmol) was added slowly with the help

of a little THF to a degassed solution of samarium diiodide (0.43 mmol, 0.1 M in THF) and HMPA (0.85 mmol) and stirred for 20 min. The reaction was then quenched with water and stirred for 10 min. Dilute HCl was added and the reaction was stirred for 30 min. The resulting mixture was extracted with ethyl acetate. The organic layer was washed with several small portions of water to remove HMPA. The organic layer was then washed with NaHCO3 (aq, sat) and NaCl (aq, sat) and dried over Na2SO4. After evaporation of the

solvents, the product was purified by column chromatography. See NMR spectra in Appendix.















APPENDIX
SPECTRAL DATA



The NMR data of selected compounds are graphically

illustrated in this appendix. The specta shown are in order of their dissertation identification number. The GO traces of diol 76 are also included in this appendix.






































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