Catalytic asymmetric electrochemical C-H functionalization of simple ketones has been developed. The transformation is realized by the combination of electrochemical oxidation and chiral primary amine catalysis. This metal- and oxidant-free method furnishes diverse C1-alkylated tetrahydroisoquinolines in high yields and with excellent enantioselectivities under very mild conditions.

Asymmetric electrochemical catalysis, an emerging frontline in asymmetric catalysis and electro‐organic synthesis, is summarized. Representative works are classified, with respect to the external chiral resources, including chiral media, chiral mediator, chiral catalyst, and chiral electrode. This concept article is expected to provide readers with the general concepts and perspectives of each chiral electrochemical catalysis mode, and to indicate the potential and future development of asymmetric electrochemical catalysis.