Enantio- and Regioselective Electrooxidative Cobalt-Catalyzed C?H/N?H Annulation with Alkenes

In recent years, the merging of electrosynthesis with 3d metal catalyzed C?H activation has emerged as a sustainable and powerful technique in organic synthesis. Despite the impressive advantages, the development of an enantioselective version remains elusive and poses a daunting challenge. Herein, we report the first electrooxidative cobalt-catalyzed enantio- and regioselective C?H/N?H annulation with olefins using an undivided cell at room temperature (up to 99 % ee). ^tBu-Salox, a rationally designed Salox ligand bearing a bulky tert-butyl group at the ortho-position of phenol, was found to be crucial for this asymmetric annulation reaction. A strong cooperative effect between ^tBu-Salox and 3,4,5-trichloropyridine enabled the highly enantio- and regioselective C?H annulation with the more challenging α-olefins without secondary bond interactions (up to 96 % ee and 97 : 3 rr). Cyclovoltametric studies, and the preparation, characterization, and transformation of cobaltacycle intermediates shed light on the mechanism of this reaction.