Alkylative Preparation of alpha-Silylalkylmagnesium from R(3)SiCHBr(2) Using a Magnesate Reagent This work was supported by a Grant-in-Aid for Scientific Research (Nos. 09450341 and 10208208) from the Ministry of Education, Culture, Sports, Science, and Technology. A.I. acknowledges the JSPS Research Fellowship for Young Scientists for financial support.

Magnesium-bromine exchange to provide the 1-bromo-1-silylmethylmagnesium species is mediated by treatment of dibromomethylsilane with an trialkylmagnesate reagent. The addition of a copper catalyst induces facile migration of an alkyl group to afford an α-silylalkylmagnesium compound, which furnishes α-silyl ketones in good yield upon treatment with acyl chloride.