Friedel-Crafts-Type Intermolecular C-H Silylation of Electron-Rich Arenes Initiated by Base-Metal Salts.

An electrophilic aromatic substitution (SE Ar) with a catalytically generated silicon electrophile is reported. Essentially any commercially available base-metal salt acts as an initiator/catalyst when activated with NaBAr(F)4. The thus-generated Lewis acid then promotes the SE Ar of electron-rich arenes with hydrosilanes but not halosilanes. This new C-H silylation was optimized for FeCl2/NaBAr(F)4, affording good yields at catalyst loadings as low as 0.5 mol %. The procedure is exceedingly straightforward and comes close to typical Friedel-Crafts methods, where no added base is needed to absorb the released protons.