Electrocatalytic π‐System Cycloadditions for Sustainable Heterocycles and Carbocycles Synthesis

ABSTRACT Electrocatalytic cycloadditions of π‐systems have emerged as versatile and sustainable strategies for constructing structurally diverse carbocycles and heterocycles. By harnessing anodic oxidation or cathodic reduction, these transformations replace stoichiometric chemical oxidants and metal catalysts with electricity as a traceless reagent, enabling environmentally benign, redox‐neutral, and atom‐economical pathways. Cycloadditions such as [2 + 1], [2 + 2], [2 + 2 + 2], [3 + 2], [4 + 2], and [5 + 2] efficiently generate cyclobutanes, cyclopentanes, cyclohexanes, and fused polycycles, often proceeding via radical‐cationic, 1,3‐dipolar, or stepwise electron‐transfer mechanisms. Mechanistic studies highlight the critical roles of radical stabilization, electrochemical potential, and substrate polarity in dictating chemo‐, regio‐, and stereoselectivity. Recent advances include multicomponent, cascade, flow‐electrochemical, and asymmetric approaches that expand structural complexity while minimizing waste. Collectively, these studies underscore the versatility of electrocatalytic cycloadditions as a green, tunable, and scalable platform for the synthesis of complex carbocyclic and heterocyclic architectures. This review positions π‐system electrocatalysis as a unifying and sustainable paradigm for constructing molecules of relevance to pharmaceuticals, agrochemicals, and materials science, highlighting its potential to replace traditional oxidants and metal‐based protocols in modern synthetic chemistry.