Trimethylsilylpotassium. Deoxygenation of epoxides with inversion of stereochemistry
- Creators
-
Dervan, Peter B.
- Shippey, Michael A.
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.
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.Additional details
- Eprint ID
- 67116
- Resolver ID
- CaltechAUTHORS:20160516-095512543
- Research Corporation
- MPS75-06776
- NSF
- Created
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2016-05-16Created from EPrint's datestamp field
- Updated
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2021-11-11Created from EPrint's last_modified field
- Other Numbering System Name
- Caltech Crellin Laboratory of Chemistry
- Other Numbering System Identifier
- 5173