Radical‐Based Convergent Paired Electrolysis

Abstract Electrochemistry offers a sustainable platform for discovering reactions involving single‐electron transfer (SET) that generates highly reactive and synthetically versatile radical species. Compared with photochemistry similarly specializing in SET which requires expensive photocatalysts, electrochemistry employs low‐cost electricity to drive the electron flow. Paired electrolysis makes use of both half‐reactions, thus obviating the need for sacrificial reactions and maximizing the atom and energy economy. In convergent paired electrolysis, anodic oxidation and cathodic reduction occur simultaneously to generate two intermediates, which are then coupled to furnish the product. It represents a distinctive approach to challenging redox‐neutral reactions. However, the gap between the two electrodes makes it hard for a reactive intermediate to come across the other coupling partner. This concept article summarizes recent state‐of‐the‐art advances on radical‐based convergent paired electrolysis, which adopted different strategies to overcome the difficulty.