Lowering the reaction temperature from 70 °C to 60 °C dramatically improved the enantioselectivity to 96.0:4.0 e.r., while maintaining a yield of 50% (Scheme 3A, Entry 5). With these results, the optimal reaction conditions proved to be a solvent mixture of i-PrOAc/n-heptane/TFE at 60 °C under constant current electrolysis (CCE) furnishing 3 in 72% yield and excellent enantioselectivity (96.0:4.0 e.r.). We further conducted a control experiment with atmospheric oxygen as the terminal oxidant. Only traces of product 3 could be detected, illustrating the indispensable role of electrolysis in the reaction outcome (Scheme 3A, Entry 7). Moreover, the reaction was equally efficient when the electrolysis was conducted under an N2 instead of an air atmosphere (Scheme 3A, Entry 8). Since we expected the hydrogen evolution reaction (HER) to be the main reduction process on the cathode, we investigated the headspace of the reaction mixture. Indeed, after completion of the reaction, molecular hydrogen could be detected by gas chromatography (Scheme 3B). Encouraged by this finding, we further quantitatively measured the gas evolution during catalysis (Scheme 3C). After completion of the reaction (~ 13 h), the yield of formed molecular hydrogen could be determined to be ≈ 80%. With the optimized reaction conditions in hand, we examined the versatility of the atropo-enantioselective electrocatalysis. A wide range of para-substituted benzamides were tolerated and furnished the corresponding C-N axial chiral products 3-12 in moderate to high yields with excellent enantioselectivities (Scheme 4A). Interestingly, for electron withdrawing substituents such as chloro-(7) or fluoro (12) groups, the electrocatalysis resulted in significantly lower yields, respectively (Scheme 4). In addition, oxidation sensitive para-MeSsubstituted benzamide provided the corresponding C-N atropoisomer 11 in high enantioselectivity which allowed the determination of the absolute configuration by single-crystal X-ray diffraction (CCDC 2415830). To our delight, varying the substitution pattern on the benzamide substrate had a significant influence on the reaction outcome. While with para-substituted benzamides high enantioselectivities were achieved, meta-and ortho-substituted benzamides resulted in significantly lower yields and enantioselectivities of the products (13-16). Nevertheless, dimethyl substituted benzamide derivative gave rise to C-N atropoisomer 17 in moderate yield and enantioselectivity. In contrast, alkyl substituents on the 3 and 4 positions of the quinoline fragment were well tolerated and provided 18 and 19, respectively. Next, the versatility of 1-alkynyl indole derivatives in the electrocatalysis was evaluated. Both, 5-MeO substituted 1-alkynyl indole as well as n-butyl-derived 1-alkynyl indole gave rise to the corresponding C-N atropoisomers 20 and 21 in high enantioselectivities (>90.0:10.0 e.r.).