Selective synthesis of functionalized, tertiary silanes by diastereoselective rearrangement-addition

Org Lett. 2005 Oct 27;7(22):4911-3. doi: 10.1021/ol0518636.

Abstract

[reaction: see text] Treatment of hydroxy-substituted silyl epoxides with Grignard reagents induces a 1,2-carbon shift to reveal alpha-silyl aldehydes, which are trapped by highly diastereoselective addition reactions of the Grignard reagent. The starting epoxides are readily accessible from propargylic alcohols by regio- and diastereoselective hydrosilylation and epoxidation reactions. In addition to providing functionalized tertiary silane products, the method is shown to offer a tertiary olefin synthesis through chemo- and diastereoselective Peterson elimination of the product tertiary silane diols.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Molecular Structure
  • Silanes / chemical synthesis*
  • Silanes / chemistry
  • Stereoisomerism

Substances

  • Silanes