Selective Synthesis of Functionalized, Tertiary Silanes by Diastereoselective Rearrangement-Addition

Org. Lett., 7 (22), 4911 -4913, 2005. 10.1021/ol0518636 S1523-7060(05)01863-8
Web Release Date: September 29, 2005

Selective Synthesis of Functionalized, Tertiary Silanes by Diastereoselective Rearrangement-Addition

Barry M. Trost,* Zachary T. Ball, and Eun-Joo Kang

Department of Chemistry, Stanford University, Stanford, California 94305-5080

bmtrost@stanford.edu

Received August 3, 2005

Abstract:

Treatment of hydroxy-substituted silyl epoxides with Grignard reagents induces a 1,2-carbon shift to reveal

-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.

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