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