(5 mol%), and bisoxazoline ligand L19 (10 mol%) at 0 °C (Table ). Gratifyingly, the reaction proceeded in a highly chemo-and regioselective manner to afford the desired cross-coupled product 7a in 78% isolated yield with 89% ee. A range of control experiments performed in the absence of the copper salt, ligand, and light irradiation confirmed that these parameters are essential for this transformation (Table ). In contrast, when the reaction was performed using ligand L10 in the presence of absence of irradiation of purple LEDs, lower yields and only moderate enantioselectivity were observed (Table ). Moreover, we carried out time-course studies on the reaction of 6a, 2a, and 3a using ligand L19 with or without visible light irradiation. It was found that the combination of Cu(CH3CN)4OTf/L19 and visible light plays an important on the conversion of oxime carbonate 2a into the relative cyanoalkyl radical, as large amount of 2a remained intact when omitting visible light irradiation (Table and Figure ). These results implied that visible-light excited copper(I)/L19 under purple LED irradiation enabled better efficiency match between cyanoalkyl radical generation and radical addition, and ensuing arylative cross-coupling with propargylic radical. Meanwhile the sterically more encumbered scaffold of L19 allowed higher enantioselectivity.