Then, a series of chiral Salox ligands bearing different substituents on the phenol moiety and the oxazoline moiety were evaluated, and L3 bearing a bulky tert-butyl group at ortho-and para-positions of the phenol moiety gave the best result affording product 3 with 94% yield and 95% ee. Lower reaction temperatures gave better enantioselectivities but also lower yields, due to the poor solubility of the ligand in polar solvents. In contrast, the use of a TFE/DCE solvent mixture dramatically increased conversion to the desired product with maintained enantioselectivity. Notably, reducing the reaction time and the amount of catalyst could still deliver the product 3 in excellent yield and enantioselectivity, highlighting the high efficiency of this electrocatalytic system (93% yield, 99% ee). Control experiments confirmed the essential role of the electricity. Moreover, cathodic proton reduction was evidenced by the detection of hydrogen through headspace GC analysis (Figure S-5 in the Supporting Information).