Enantioselective Construction of Single and Vicinal All-Carbon Quaternary Stereocenters through Ion-Pair-Catalyzed 1,6-Conjugate Addition.

An asymmetric 1,6-conjugate addition to presynthesized δ-aryl-δ-cyano-disubstituted para-quinone methides through bifunctional phosphonium-amide-promoted ion-pair catalysis for acyclic all-carbon quaternary stereocenter construction has been described. Both acyclic and cyclic 1,3-dicarbonyls participate in the asymmetric alkylation reaction, furnishing a wide array of diarylmethanes bearing a single acyclic quaternary carbon stereocenter or vicinal cyclic and acyclic quaternary carbon stereocenters with high efficiency and excellent stereoselectivity. Computational studies elucidate the origin of the enantioselectivity.