Abstract
With 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 oC),
an eternal-ligand-free system (Ni/t-BuOK) can efficiently facili-tate
the 3,4-anti-Markovnikov hydrosilylation to provide homoallylic silanes
via electrophilic activation process; under room temperature (25 oC), 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
regioselec-tivities.