The Discovery and Development of an Iridium‐Catalyzed N→C Alkyl Transfer Reaction

Abstract Under Ir‐catalyzed conditions, N ‐2°‐alkyl or N ‐3°‐alkyl substituents of diverse tertiary aryl amides can be exchanged with the ortho ‐aryl C─H bond of the aromatic unit. These alkyl transfer processes employ a homochiral diphosphonite ligand, and this enforces notable levels of enantioconvergency for non‐stereodefined 2°‐alkyl substituents. Related processes allow the intermolecular transfer of N ‐2°‐alkyl substituents, providing a convenient means of introducing difficult‐to‐install ortho ‐alkyl units.