A set of mechanistic experiments was carried out to rationalize the electrocatalytic modus operandi and to understand the exact role of electricity. First, the stoichiometric electrochemical preparation of the cyclometallated, C-H activated complex Co(III)-C1 was achieved under galvanostatic conditions (Fig. ), which was isolated and fully characterized. Stoichiometric transformations of complex Co(III)-C1 showed that the electricity was required for efficient and selective product formation (Fig. and Table ). This observation can be rationalized with an oxidationinduced reductive elimination. High-resolution mass spectrometric studies (Fig. and Fig. ) and UV-vis spectroelectrochemical analysis (Fig. -9, Fig. ). A nonlinear effect (NLE) study was also performed, and a linear relationship was found (Table , Based on the findings of the cobaltaelectro-catalyzed spirocyclization (Fig. ), we continued our studies with unactivated alkenes, where instead of the spiroannulation, alkene carboamination was observed representing a complementary reactivity and salicyloxazoline ligands proved to be powerful for the desired enantioselective transformation (Fig. ). In the optimization studies, the L-valinol derived ligand L3 was identified as optimal and allowed the synthesis of various chiral dihydroisoquinolinones 25-32 at room temperature with outstanding enantiomeric as well as diastereomeric purity and high yield (Fig. ). In addition to functional groups at different positions on the benzamide and heteroarene derived amide , heteroatom-containing cyclic alkene was also well tolerated , albeit L4 was found to be the most suitable ligand in the latter case. The X-ray crystallographic analysis of 32 defined the absolute configuration of the product (see Supplementary Materials, page 112). To determine whether enantioselective cobaltaelectrocatalysis in addition to point chiral molecules can yield axially chiral molecules, the benzamide 34 was reacted with the 4-hydroxyalkynoate 35 to afford the product 36 in a C-H/N-H cascade annulation. Delightfully, the desired product 36 could be isolated in high enantiomeric excess and the structure was confirmed by X-ray crystallographic analysis (Fig. ). The atropostability of the C-N axis was calculated to estimate the time frame of racemization, where a rotational barrier of 48.3 kcal/mol was found, resulting in an exceptionally high atropostability having a half-life t1/2 25°C of 3.2•10 18 years (Fig. and Table , Fig. ). In the optimization of the reaction parameters, i-PrOH was found to be a particularly suitable solvent for the atropoenantioselective transformation, in which the product 36 is formed using ligand L5