Electroreductive Dynamic Kinetic Resolution for Constructing Central and Axial Chirality †

Comprehensive Summary Asymmetric electrosynthesis has emerged as a powerful tool for assembling chiral molecules, yet concurrently building multiple stereogenic elements, such as central and axial chirality, has been rarely reported. The difficulty mainly originates from hard‐to‐control high‐energy reactive intermediates and poor compatibility between polar electrolytic environments and chiral catalytic systems. Dynamic kinetic resolution (DKR), which takes advantage of fast in‐situ interconversion between stereoisomers, offers an attractive pathway to access highly enantioenriched products, but its implementation under electroreductive conditions is still underexplored. Herein, we describe a nickel‐catalyzed electroreductive dynamic kinetic resolution to realize enantioselective cross‐coupling between racemic aryl triflates and aldehydes. Relying on a newly synthesized indane‐based PyrOx derivative ligand, this direct electrolysis method efficiently furnishes chiral heterobiaryl secondary alcohols with simultaneous generation of axial and central chirality, delivering high diastereoselectivity (dr > 19:1) and excellent enantioselectivity (up to 99% ee). A 1.0 mmol scale‐up experiment further validates its synthetic practicability. Additive sodium iodide mitigates anode passivation, stabilizing electrolysis and improving reaction performance. Mechanistic investigations rule out radical‐dominated pathways and support a monomeric nickel‐ligand complex governing enantiodetermining steps. This work expands the scope of asymmetric electrochemistry and provides a complementary strategy for constructing complex central and axial chirality molecules.