Copper-Catalyzed Silylation of C(sp3)-H Bonds Adjacent to Amide Nitrogen Atoms.

A copper-catalyzed C-Si bond formation between N-halogenated amides and Si-B reagents is described. This oxidative coupling enables the silylation of C(sp3)-H bonds α to an amide nitrogen atom. The utility of the new method is demonstrated for sulfonamides, and N-chlorination with tBuOCl and C-H silylation employing CuSCN/4,4'-dimethoxy-2,2'-bipyridine as catalyst can be performed without purification of the N-Cl intermediate.