Ir‐Catalyzed C−H Amidation of Aldehydes with Stoichiometric/Catalytic Directing Group

Abstract Ir‐catalyzed sp 2 C−H amidation of aldehydes with various anilines as stoichiometric or catalytic directing groups was accomplished. A wide range of substrates were selectively amidated in good to excellent yields with broad functional group tolerance. The iridacycle complexes were isolated, characterized, and proved as key intermediates. Kinetic studies and Hammett plots provided detailed understandings of this amidation. According to the mechanism, the electron‐rich ArSO 2 N 3 was proved effective for intermolecular sp 3 C−H amidation.