Metal-free synthesis of gem-silylboronate esters and their Pd(0)-catalyzed cross-coupling with aryliodides

Abstract

A transition-metal-free method for the synthesis of gem-silylboronate esters with arylboronic acids and trimethylsilyldiazomethane (TMSCHN₂) has been developed. This transformation is a straightforward homologation of arylboronic acids and features wide substrate scope and good functional-group tolerance. The gem-silylboronate esters undergo efficient Suzuki–Miyaura cross-coupling with aryliodides and the silyl group of the product can be further functionalized. Tertiary carbon centers with different substituents can be constructed successfully by selective and sequential functionalization.