Selective synthesis of functionalized, tertiary silanes by diastereoselective rearrangement-addition.
[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.
Trost
Barry M
BM
Department of Chemistry, Stanford University, California 94305-5080, USA. bmtrost@stanford.edu
Ball
Zachary T
ZT
Kang
Eun-Joo
EJ
D015394:Molecular Structure; D012821:Silanes / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D012821:Silanes