N-heterocyclic pyridylmethylamines: Synthesis, complexation, molecular structure, and application to asymmetric Suzuki-Miyaura and oxidative coupling reactions

Abstract

The synthesis of N,N-bidentate ligands based on a π-deficient N-heterocyclic pyridylmethylamine core is described. The preparation and characterization of the corresponding N,N-ligand-palladium complexes in solution and the solid state are illustrated. Pd complexes showed a good yield and moderate catalytic activity (up to 40% ee) in the asymmetric Suzuki-Miyaura coupling reaction, leading to methoxybinaphthyl derivatives. The combination of N,N-pyridylmethylamines with cuprous iodide revealed effective catalytic systems in oxidative naphthol derivative coupling reactions, affording the corresponding binaphthyls in high yields and with enantioselectivities of up to 61%. © 2011 American Chemical Society.