Enantioselective Copper-Catalyzed Allylic Substitution Reaction with Aminohydroxyphosphine Ligand

A proline-derived aminohydroxyphosphine ligand induced excellent regio- and enantioselectivities (S(N)2':S(N)2>94:6, 94-97% ee) in the copper-catalyzed substitution reaction of cinnamyl phosphates with Et2Zn. A computational modelling, study of the reaction pathway suggests that the displacement of the leaving group takes place In an ordered, anti-fashion through simultaneous copper-olefin and zinc-oxygen interactions, which is critical for the enantioselection.