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(sp2)–H bond activation.