Transition metal-catalyzed reactions of silacyclobutanes with a variety of π units have attracted much attention and become one of the most straightforward and efficient approaches to rapidly access structurally diverse organosilicon compounds. However, the reaction of silacyclobutanes with alkynes still suffers from some limitations: (1) internal alkynes remain challenging substrates; (2) expensive Pd- or Rh-based catalysts have been employed in all existing systems; (3) controlling chemodivergence has not yet been realized. Herein we realize Ni-catalyzed chemodivergent reactions of silacyclobutanes with alkynes. In comparison with the previous Pd or Rh catalytic systems, our Ni-catalytic system features: 1) complementary substrate scope; 2) ligand-controlled chemodivergence; 3) low cost. The ligand precisely dictates the pathway selectivity, leading to the divergent formation of (benzo)silacyclohexenes and allyl vinylsilanes. Moreover, we demonstrate that employment of a chiral phosphine ligand is capable of forming silicon-stereogenic allyl vinylsilanes in high yields and enantioselectivities. In addition, DFT calculation is performed to elucidate the origin of the switchable selectivities, which is mainly attributed to different ligand steric effects.
© 2022. The Author(s).