Rh(III) and Ir(III)Cp* Complexes Provide Complementary Regioselectivity Profiles in Intermolecular Allylic C–H Amidation Reactions

An efficient regioselective allylic C–H amidation of mono-, di-, and trisubstituted olefins has been developed. Specifically, the combination of dioxazolone reagents with RhCp* and IrCp* catalysts is reported to promote reactions with complementary regioselectivites to those previously observed in Pd-catalyzed and Ag-promoted Rh-catalyzed reactions. We report that catalyst matching with substrate class is essential for selective reactions. RhCp* complexes are required for high conversion and selectivities with β-alkylstyrene substrates, and IrCp* complexes are necessary in the context of unactivated terminal olefins.