We then examined the amide substrate scope. As shown in the Scheme 3, a wide range of aromatic amides with electron-donating group (Me, OMe) and electronwithdrawing group (F, Cl, Br, and CF3) can react with alkylarene to yield benzylic C(sp 3 )-H amination products (4a-4h) in moderate to good yields (56-71%) with excellent enantioselectivities (95:5-97:3 er). Furthermore, the heteroaromatic amides (bearing a pyridine, or furan, or thiophene) could also undergo the reaction to afford the amination products (4j-4l) in moderate yields with good to excellent enantioselectivities (up to 96:4 er). The reaction of 3-pyridylamide is noteworthy because the coordination of pyridinyl group to copper is strong ad usually prevent catalysis. Moreover, aliphatic amides can also be applied to the reaction, affording the corresponding amination products (4m-4o) with high enantioselectivities (95:5-97:3 er). To illustrate the synthetic utility of the reaction, we carried out the transformations of the amination products and synthesis of chiral drugs (Scheme 4). The amide 3j was deprotected to chiral primary amine by using Schwartz reagent at mild conditions without losses of enantiomeric purity (Scheme 4A). The clinically used chiral drugs tecalcet (8), a calcimimetic compound for the treatment of hyperparathyroidism, 14 dapoxetine (11) for the treatment of premature ejaculation, and rivastigmine (14) for the treatment of Alzheimer's disease 16 were readily prepared by using the enantioselective amination as the key steps (Scheme 4B). Also, the SARS-CoV PLpro inhibitor 17 (15) was synthesized in one step. The syntheses of these chiral drugs and biologically active molecules further demonstrated that this amination reaction is a powerful method for the synthesis of chiral compounds containing a benzylic amine moiety.