A DMAP-enabled strategy for C(sp2)-Si coupling of halosilanes with organic halides

Organosilanes find extensive utility in numerous fields, and thus attract significant interest in methodological developments for their synthesis. Conventional approaches predominantly rely on nucleophilic substitutions using pre-synthesized and highly reactive organometallic reagents. While recent advances in the coupling of commercial carbon electrophiles with halosilanes circumvent the need for these sensitive nucleophiles, such systems often require meticulously optimized catalysts, and the applicability of substrate scope often differentiates case-by-case. Herein, we report a general and robust 4-(dimethylamino)pyridine-enabled platform for C(sp²)-Si bond formation between organic halides and halosilanes. Combined experimental and computational studies reveal a dual role of DMAP in activating both inert Csp²-X (X = Br, I, Cl) and Si-Cl bonds, where DMAP enables the zincation of aryl halides, and also activates the Si-Cl bonds via hyper-valent silicate species, and a followed-up coupling of both species furnished the silylation process.