Mechanism of Catalytic Functionalization of Primary C-H Bonds Using a Silylation Strategy

The mechanism of Ir-catalyzed gamma-functionalization of a primary sp(3)(C-H) bond in 2-methyl cyclohexanol is examined using the density functional theory (M06). The nature of the active catalyst for the initial silylation of alcohol is identified as the monomer derived from [Ir(cod)OMe](2) while that for gamma-sp(3)(C-H) activation leading to oxasilolane is (IrH(nbe)(phen)]. The rate-determining step is found to involve Si-C coupling through reductive elimination.