Boron Catalysis-Enabled Regioselective Ring-Retentive Hydrosilylation of Methylenecyclopropanes

Herein, we report the highly regioselective ring-retentive hydrosilylation of methylenecyclopropanes (MCPs) with hydrosilanes by a B(C₆F₅)₃ catalyst. The catalytic protocol affords an atom-efficient route for the synthesis of silylcyclopropanes, featuring 100% atom-efficiency, broad substrate scope (42 examples), mild conditions, and high regio-, and chemoselectivity. The current metal-free catalytic hydrosilylation also provides a complementary pathway for the synthesis of structurally diverse organosilicon compounds from MCPs over transition metal-catalyzed variants.