Copper‐Catalyzed Site‐Selective Intramolecular Amidation of Unactivated C(sp3)H Bonds

Abstract The intramolecular dehydrogenative amidation of aliphatic amides, directed by a bidentate ligand, was developed using a copper‐catalyzed sp 3 CH bond functionalization process. The reaction favors predominantly the CH bonds of β‐methyl groups over the unactivated methylene CH bonds. Moreover, a preference for activating sp 3 CH bonds of β‐methyl groups, via a five‐membered ring intermediate, over the aromatic sp 2 CH bonds was also observed in the cyclometalation step. Additionally, sp 3 CH bonds of unactivated secondary sp 3 CH bonds could be functionalized by favoring the ring carbon atoms over the linear carbon atoms.