Enantioselective total syntheses of complex natural and designed molecules were accomplished by asymmetric reactions.1.Efficient Ni-catalyzed regioselective enantioselective intramolecular reductive cyclization of aza-alkynones catalyzed by novel P-chiral bisphosphorus ligand DI-BIDIME was achieved with 1000 TON of Ni(cod)2 and 99:1 er is developed.