Regiodivergent Dehydrosilylation of Alkenes via Ligand-Gated Conformational Restriction

Dehydrosilylation of alkenes offers a direct route to valuable vinylsilanes or allylsilanes. Although established methods exist, achieving regiodivergent dehydrosilylation from identical substrates within a single catalytic system remains unknown. Herein, we report a regiodivergent dehydrosilylation of alkenes enabled by a single ligand type (OIP). Key to this regiocontrol is ligand-gated conformational restriction. By altering the modification sites on the OIP ligand, the rotation of a specific C–C bond is restricted, thereby confining β-H elimination to a single direction. This method leads to the practical assembly of vinylsilanes and allylsilanes in generally moderate to good yields. Substrates bearing both aryl and alkyl substituents underwent the reaction smoothly. The gram-scale reactions proceed smoothly to deliver the target products with good regioselectivity.