Harnessing Alkene Radical Anions via Electroreduction Strategy: An Emerging Paradigm for Alkene Functionalization

Alkene‐derived radical anions represent a unique and versatile class of reactive intermediates with extensive applications in synthetic chemistry for constructing diverse structurally and synthetically valuable organic molecules. These intermediates exhibit dual reactivity because they possess both carbon radical and anionic characters, thus offering new opportunities and attractive paradigms for the divergent functionalization of alkenes. Conventional generation of alkene radical anions relies heavily on stoichiometric reductants, which often suffer from poor selectivity, limited substrate scope, and the formation of undesired byproducts. This has motivated the exploration of robust and sustainable alternative strategies. In recent years, electrocatalysis has emerged as a promising and efficient synthetic tool, providing a synthetically attractive and environmentally friendly alternative for the single‐electron reduction of alkenes. This review primarily focuses on electrochemically generated alkene radical anions and their pivotal role in enabling alkene functionalization, and systematically elaborates on their formation mechanisms. The objective of this review is to offer a comprehensive picture of the current state of the field, enhance the understanding of this chemical paradigm, and inspire innovative research to promote broader innovative applications of electrocatalytic alkene radical anion chemistry.