While the predicted direction matches the experimental outcome, the magnitude of the difference remains significant, likely due to the differences between the training set's temperature and solvent conditions from the validation conditions for the scope, compared to the training data from mono atropoisomers solely. Indeed, the developed cobalt electrocatalysis was applicable, and 7-substituted quinolinamides furnished the desired products (22-24) featuring two chiral C-N axes in moderate to high yields (up to 82%) with excellent enantio-and diastereoselectivities (up to 99.5:0.5 e.r., >20:1 d.r.). This methodology also allows the tolerance of valuable ester (23) and morpholine amide (24) functionalities on the 2-position of the 1-alkynyl indole. Next, the atropo-stability of the products was examined. For this, 3 was heated up to 200 °C for 24 h. No racemization was observed, and the enantiomeric ratio was maintained (96.0:4.0 e.r., see supporting information). Therefore, 3 shows high atropo-stability at room temperature, and the energy barrier of rotation was determined to be 64.8 kcal mol -1 according to DFT calculations (see supporting information). To investigate the reaction mechanism, the cyclometallated cobalt(III)-complex Co III -UL1 with 4-methoxypyridine as a stabilizing ligand was prepared (Scheme 5A). Subsequently, a stoichiometric reaction between the chiral cobaltacycle Co III -UL1 and 1-alkynyl indole 2 was performed. The desired product 3 was formed in 43% yield and similar enantioselectivity (95.5:4.5 e.r.) without electricity under a nitrogen atmosphere (Scheme 5A). This shows that reductive elimination proceeding from cobalt(III) intermediate is feasible and no further oxidation to cobalt(IV) is necessary. Furthermore, the cobalt electrocatalysis was analyzed by cyclic voltammetry (Scheme 5B). While Co(OAc)2•4H2O showed no redox activity in the solvent system during catalysis, the addition of UL1 resulted in a new reversible oxidation event at 0.95 V vs the standard calomel electrode (SCE). This oxidation event becomes significantly more prominent in the presence of benzamide 1, further supporting a cobalt(II/III) regime. In addition, we performed intermolecular competition experiments between substrates 1 and [D5]-1. No kinetic isotope effect (KIE) was observed, indicating the C-H cleavage was not rate-determining (Scheme 5C). Next, we investigated the possibility of transforming the tosyl-group of 3. We found that 3 could be easily converted to desulfonylated derivative 26 using nickel/phosphine catalysis without racemization (Scheme 5D).