Iridium-Catalyzed Allylic Alkylation Reaction with N-Aryl Phosphoramidite Ligands: Scope and Mechanistic Studies

A series of N-aryl phosphoramidite ligands has been synthesized and applied to iridium-catalyzed allylic alkylation reactions, offering high regio- and enantioselectivities for a wide variety of substrates. These ligands feature the synthetic convenience and good tolerance of the ortho-substituted cinnamyl carbonates. Mechanistic studies, including DFT calculations and X-ray crystallographic analyses of the (π-allyl)-Ir complexes, reveal that the active iridacycle is formed via C(sp(2))-H bond activation.