The reactions of tris(trimethylsilyl)methyl-lithium with some carbon electrophiles

Abstract

Tris(trimethylsilyl)methyl-lithium (1) reacts with non-enolisable aldehydes, ketones, and acid chlorides, and with some epoxides, with the formation of carbon–carbon bonds. This method of preparing functionalized silanes is limited by the readiness with which (1) abstracts a proton, if one is available, rather than attacks at carbon. In the reaction with epoxides, the product alkoxide can transfer a silyl group from carbon to oxygen, and in one case the intermediate so formed reacts to give a cyclopropane (32) in what is a homologue of the Peterson reaction. The 1,4-transfer of a silyl group occurs in other systems when the resulting carbanion is stabilised by such groups as phenylthio and diphenylphosphinoyl.