The Electrochemical Frontier in Asymmetric Synthesis: Forging Challenging Quaternary Stereocenters

Quaternary carbon stereocenters can be widely found in natural products, chiral pharmaceuticals, and functional materials, which stereocontrolled construction remains one of the most formidable challenges in asymmetric catalysis. Organic electrosynthesis, which uses electrons as traceless redox reagents, enables the precise generation and controlled conversion of highly reactive intermediates under mild conditions, thereby providing a green and efficient platform for the assembly of these congested stereocenters. This review highlights recent advances in the electrochemical asymmetric construction of quaternary stereocenters and offers a systematic overview of this rapidly emerging area. Organized according to substrate classes and reaction design principles, with mechanism/activation mode introduced as a secondary classification criterion, the discussion focuses on four major strategies based on sp 2 ‐hybridized prochiral substrates: functionalization of poly‐substituted alkenes, transformation of prochiral enolates, nucleophilic addition to carbonyl compounds, and nucleophilic addition to imine derivatives. In addition, two distinctive approaches, namely indole dearomatization and electrochemical kinetic resolution, are summarized with emphasis on reaction mechanisms, modes of chiral induction, and substrate scope. The review further analyzes the key challenges that continue to limit this field, including catalyst development, expansion of reaction manifolds, and practical translation to large‐scale synthesis. Finally, future directions and opportunities are discussed with the aim of promoting the broader application of asymmetric electrochemical synthesis in the preparation of complex chiral molecules and the development of chiral pharmaceuticals.