Mechanistic Exploitations of the Asymmetric α-Allylation of an α-CF 3 Amide Enabled by Cu/Pd Synergistic Dual Catalysis.

DFT computational investigations were carried out to explore the mechanism of enantioselective Cu/Pd-catalyzed allylation of an α-CF 3 amide. A kinetically favored chiral Cu(I)-enolate species undertakes facile allylation with racemic π-allyl-Pd(II) species to stereoconvergently deliver a stereocenter. Computational models and distortion/interaction analyses unveil versatile modes of stereoinduction wherein the reactive site of ( R,R p )-Walphos/copper(I)-enolate cis to the -PPh 2 moiety has more space for the nucleophilic reaction, and can face-selectively capture π-allyl-palladium(II) intermediates using sterically affected distortions.