Iridium(III)‐Catalyzed Regioselective Intermolecular Unactivated Secondary Csp 3 −H Bond Amidation

For the first time, a highly regioselective intermolecular sulfonylamidation unactivated secondary Csp 3 −H bond has been achieved using Ir III catalysts. The introduced N , N ’‐bichelating ligand plays a crucial role in enabling iridium–nitrene insertion into a secondary Csp 3 −H bond via an outer‐sphere pathway. Mechanistic studies and density functional theory (DFT) calculations demonstrated that a two‐electron concerted nitrene insertion was involved in this Csp 3 −H amidation process. This method tolerates a broad range of linear and branched‐chain N ‐alkylamides, and provides efficient access to diverse γ‐sulfonamido‐substituted aliphatic amines.