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Trimethylsilylpotassium. Deoxygenation of epoxides with inversion of stereochemistry

Dervan, Peter B. and Shippey, Michael A. (1976) Trimethylsilylpotassium. Deoxygenation of epoxides with inversion of stereochemistry. Journal of the American Chemical Society, 98 (5). pp. 1265-1267. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20160516-095512543

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Abstract

The reactions of silyl anions with appropriately substituted epoxides are potential stereospecific routes to diastereomerically pure erythro and threo-/3-alkoxysilanes. We report here that some mono-, di-, and trisubstituted epoxides can be deoxygenated in good yields stereospecifically with inversion of stereochemistry by trimethylsilylpotassium generated in situ. Reaction of cis and trans epoxides with hexamethyldisilane and potassium methoxide (KOMe) in anhydrous hexamethylphosphoric triamide (HMPT) at 65° under argon for 3 h affords the corresponding trans and cis olefins, respectively. Since olefins can be epoxidized with retention of stereochemistry, this constitutes a new olefin inversion procedure. The yields and stereospecificity of this deoxygenation reaction for several isomerically pure (>99%) epoxides5 are listed in Table I.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja00421a039DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja00421a039PublisherArticle
ORCID:
AuthorORCID
Dervan, Peter B.0000-0001-8852-7306
Additional Information:© 1976 American Chemical Society. Received September 25, 1975. Publication Date: March 1976. The authors are grateful to the Research Corporation and the National Science Foundation (MPS75-06776) for their generous support of this work. We are grateful for stimulating discussions with Professors David A. Evans and Dieter Seebach during the course of this research.
Funders:
Funding AgencyGrant Number
Research CorporationUNSPECIFIED
NSFMPS75-06776
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Caltech Crellin Laboratory of Chemistry5173
Issue or Number:5
Record Number:CaltechAUTHORS:20160516-095512543
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160516-095512543
Official Citation:Trimethylsilylpotassium. Deoxygenation of epoxides with inversion of stereochemistry Peter B. Dervan and Michael A. Shippey Journal of the American Chemical Society 1976 98 (5), 1265-1267 DOI: 10.1021/ja00421a039
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:67116
Collection:CaltechAUTHORS
Deposited By: Victoria Brennan
Deposited On:16 May 2016 22:04
Last Modified:03 Oct 2019 10:03

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