and SL5), N,P-ligand (SL3), and P,P-ligand (SL4) were found to be ineffective. We reasoned that the hard nature of O,O-type chiral ligand would be more suitable for copper ions according to the classical HSAB (Hard-Soft-Acid-Base) principle. To improve the enanticontrol and diminish the undesired di-alkynylated product, we further evaluation the reaction temperature. Notably, the reaction maintained good reactivity even when the reaction temperature was decreased to 0 o C. The ee value of 3aa was improved to 93% and the di-alkynylation reaction was significantly restrained (3aa', 4%) (Scheme 1a). Several BINOL-derived O,O-bidentate ligands (L2 to L8) were further screened under prolonged reaction time (24 h) and the simple (S)-BINOL (L1) led to the optimal results, giving 3aa in 66% yield with 93 ee and only 6% yield of undesired 3aa' (Scheme 1b). Interestingly, L6 bearing bulky 3,5-di-Me-phenyl group at the 3,