Ligand-Controlled On–Off Switch of a Silicon-Tethered Directing Group Enabling the Regiodivergent Hydroalkylation of Vinylsilanes under Ni–H Catalysis

A regiodivergent Ni–H-catalyzed hydroalkylation of vinylsilanes is described. Depending on the ancillary ligand at the nickel catalyst, the regioselectivity can be steered by a directing group attached to the silicon atom. The mild protocols allow for the selective synthesis of either branched or linear alkylsilanes. An example of a vinylgermane is also reported. The method features a broad scope with high functional-group tolerance and follows a radical mechanism.