Lewis base-promoted carbon-carbon sp³-sp³ coupling reactions of α-silyl silylethers

A Lewis base-promoted addition of α-silyl silylethers to primary halides has been developed. This new carbon-carbon sp³-sp³ bond-forming process accesses an unconventional reactivity pattern (d ¹ synthon) from easily accessible precursors. The strategy accommodates a variety of primary alkyl, allylic and benzylic electrophiles and α-silyl silylethers. These d¹ synthons have also been used in the synthesis of cross pinacol and benzil products. Mechanistic studies indicate significant intermolecular silyl group exchange during the reaction.