The substituent redistribution
of hydrosilanes on silicon through
C–Si and Si–H bond cleavage and reformation is of great
interest and importance, but this transformation is usually difficult
to achieve in a selective fashion. By using electron-rich aromatic
hydrosilanes, we have achieved for the first time the selective C–Si/Si–H
bond homo- and cross-metathesis of a series of hydrosilanes in the
presence of a boron catalyst B(C6F5)3. This protocol features simple reaction conditions, high chemoselectivity,
wide substrate scope, and high functionality tolerance, offering a
new pathway for the synthesis of multisubstituted functional silanes.