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.