and di-functionalization are also long-term hurdles, which are detrimental to stereocontrol. We reported herein a copper-catalyzed enantioselective C-H alkynylation with terminal alkynes assisted by 8-aminoquinoline DG using readily available (S)-1,1'-bi-2,2'-naphthol [(S)-BINOL] as chiral ligand (Figure ). The reaction proceeded under mild conditions with catalytic amount of coper salt, providing a broad range of chiral ferrences in good yields and enantioselectivities (0 o C, 37 examples, up to 77% yield and 94% ee). The alteration of stoichiometric chemical oxidant with renewable electricity in an operationally simple undivided cell is also feasible (room temperature, up to 76% yield and 93% ee), demonstrating the robustness of this copper/BINOL catalysis. Gram-scale synthesis, versatile synthetic transformations, and application of the resulting oxazoline-olefin ligand in asymmetric synthesis also highlight the utility of the protocols.