Palladium-Catalyzed C–H Silylation of Aliphatic Ketones Using an Aminooxyamide Auxiliary

Abstract

A palladium-catalyzed β-C(sp3)-H silylation of aliphatic ketones with disilanes to afford β-silyl ketones is reported. The aminooxyamide auxiliary is critical for the C-H activation and silylation. The reaction tolerates a number of functional groups and shows good selectivity in silylating β-C(sp3)-H bonds in the company of C(sp2)-H bonds and acidic α-C(sp3)-H bonds. The reaction is scalable, and the aminooxyamide auxiliary is readily removed to give β-silyl ketones, which could serve as useful building blocks for organic synthesis. Late-stage diversification using this protocol is demonstrated in the silylation of santonin with good yield.