Nickel-catalyzed silylation of aryl thianthrenium salts with silylzinc pivalates

A nickel-catalyzed C–S silylation of aryl thianthrenium salts with salt-stabilized silylzinc pivalates is disclosed, thus allowing us to rapidly incorporate silyl motifs into aromatics in a site- and chemoselective fashion. This method is distinguished by its ample scope and facile derivatizations of the aryl silanes for increasing functional molecular complexity. Moreover, modular installation of silyl groups into pharmaceutically active molecules provides a new platform for the synthesis of sila-drugs.