Enantioselective Synthesis of Disilacyclohexenes via Nickel-Catalyzed Asymmetric Reductive [4 + 2] Sila-Cycloaddition

So far, numerous asymmetric hydrosilylation reactions have been reported, the asymmetric reductive cross-coupling of chlorosilanes with other electrophiles or alkenes to synthesize chiral organosilicon compounds has yet to be documented. In this study, we report a nickel-catalyzed asymmetric [4 + 2] sila-cycloaddition reaction that efficiently produces disilacyclohexenes with good yields and enantioselectivities of up to 99% ee. Additionally, we synthesized various achiral cyclic disilanes and digermanes to demonstrate the reaction’s applicability. Mechanistic studies, based on Hammett analysis, revealed that the enantioselectivities are determined by the homolysis and recombination of the Ni–C bond.