Nickel‐Catalyzed Regioselective Hydrosilylation of Conjugated Dienes†

Abstract

Comprehensive SummaryWith the increasing demand for homoallylic silanes and allylic silanes, the highly efficient and regioselective hydrosilylations of conjugated dienes are urgently needed. Herein, we developed a Ni‐catalyzed regiodivergent hydrosilylation of aromatic conjugated dienes by adjusting the temperature and ligands. Under low temperature (–30 °C), an eternal‐ligand‐free system (Ni/t‐BuOK) can efficiently facilitate the 3,4‐anti‐Markovnikov hydrosilylation to provide homoallylic silanes via electrophilic activation process; under room temperature (25 °C), a ligand‐controlled system (Ni/t‐BuOK/PPh3) can eventuate the 3,4‐Markovnikov hydrosilylation to produce allylic silanes via Chalk‐Harrod process. Both systems are compatible with various conjugated dienes and primary silanes in excellent yields and regioselectivities.