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.

A method for catalytic intermolecular allylic C-H amination of trans-disubstituted olefins is reported. The reaction is efficient for a range of common nitrogen nucleophiles bearing one electron-withdrawing group, and proceeds under mild reaction conditions. Good levels of regioselectivity are observed for a wide range of electronically diverse trans-β-alkyl styrene substrates.

Am ethod for catalytic intermolecular allylic C À H amination of trans-disubstituted olefins is reported. The reaction is efficient for ar ange of common nitrogen nucleophiles bearing one electron-withdrawing group,a nd proceeds under mild reaction conditions.Good levels of regioselectivity are observed for awide range of electronically diverse trans-balkylstyrene substrates.