N-Heterocyclic Pyridylmethylamines: Synthesis, Complexation, Molecular Structure, and Application to Asymmetric Suzuki-Miyaura and Oxidative Coupling Reactions

The synthesis of N,N-bidentate ligands based on a pi-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% cc) 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%.