To our delight, the reaction of 1a with 2c in an operationally simple undivided cell equipped with a reticulated vitreous carbon (RVC) anode and a platinum cathode at ambient temperature allowed us to provide the desired product 3ac in good yield and enantioselectivity (76% yield, 91% ee) after slightly adjusting the reaction parameters (Table ), and the undesired dialkynylated product was obtained in only 7% yield. Then, to compare with the results obtained through chemical oxidation, representative substrates were explored under enantioselective electrochemical conditions (Scheme 3). Generally, the reaction proceeded efficiently to give the desired planar chiral products in good yields with high levels of enantiocontrol and only trace of dialkynylated products could be observed. Notably, alkynes bearing heteroaromatic (2bb, 2cc) and alkyl (2gg, 2hh) substituents were also compatible, giving the desired products in satisfactory results. In addition, ferrocenecarboxamides bearing diverse substituents, including acyl and alkyl, on the other Cp ring underwent C-H alkynylation smoothly, providing the planar chiral products (3gc, 3oc, 3rc, 3st, 3ta) in moderate yields (50% to 72%) with good enantioselectivities (80% to 87% ee). The absolute configuration of 3oc was unanimously assigned by single-crystal X-ray diffraction analysis. Mechanistic insights