Abstract
Efficient catalytic protocols for C-H silylations of arenes and heteroarenes with sterically and electronically different hydrosiloxysilanes are disclosed. The silylations are catalyzed by a well-defined Rh-complex (1 mol%), derived from [Rh(1,5-hexadiene)Cl](2) and a bulky BINAP type ligand. This catalyst not only promotes C-Si bond formation affording the desired products in up to 95% isolated yield, but also can suppress the silane redistribution side reactions of HSiMe(2)(OTMS). The protocol can also be applied for the C-H silylations of more reactive HSiMe(OTMS)(2) with a much lower catalyst loading (0.25 mol%) and even with sterically demanding HSi(OTMS)(3). The steric bulk of the arene substituent and hydrosiloxysilane is a major factor in determining the regioselectivity and electronic effect as secondary. The current method can be performed under operationally diverse conditions: with/without a hydrogen scavenger or solvent.