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.