Enantioselective Intermolecular Radical Amidation and Amination of Benzylic C−H Bonds via Dual Copper and Photocatalysis

A method for direct access to enantioenriched benzylic amides and carbamate‐protected primary benzylamines by C−H functionalization is reported. The C−H substrate is used as limiting reagent with only a small excess of the unactivated amide or carbamate nucleophile. The enantioselective intermolecular dehydrogenative C−N bond formation is enabled by a combination of a chiral copper catalyst, a photocatalyst, and an oxidant, and it takes place under mild conditions, which allow for a broad substrate scope. The method is compatible with late‐stage C−H functionalization, and it provides easy access to 15N‐labeled amides and amines starting from cheap 15NH4Cl. A method for enantioselective intermolecular benzylic C−H amidation and amination is reported. This dehydrogenative C−N bond formation displays broad substrate scope and good atom economy, is amenable to late‐stage C−H functionalization, and enables easy access to 15N‐labeling from cheap [15N]‐NH4Cl.