Iridium-Catalyzed Asymmetric Allylic Amination Reactions with N‑Aryl Phosphoramidite Ligands

A series of N-aryl phosphoramidite ligands were synthesized, and the iridium complexes derived from these novel ligands were proven to be efficient catalysts for asymmetric intermolecular allylic amination reactions. This C–N bond forming process readily accommodates a diverse range of amines and allylic carbonates, especially for the previously challenging ortho-substituted cinnamyl substrates. Moreover, isolation and characterization of the corresponding (π-allyl)–iridium complex K1 reveal that the active iridacycle is generated through a C­(sp2)–H bond insertion of tetrahydroquinoline of the ligand.