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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. [ABSTRACT FROM AUTHOR]

An electrophotochemical dual metal‐catalyzed protocol for decarboxylative arylation of simple aliphatic carboxylic acids with aryl halides is reported. The relative stabilities of catalytically active metal complexes simultaneously generated at anode and cathode are the key design elements for the success of this convergent paired electrolysis. This new electrophotocatalytic method is mild, robust, and most importantly, capable of accommodating simple primary aliphatic acids including acetic acid – ubiquitous and variegated structural motifs yet remain oddly challenging substrates – directly as native functional groups for decarboxylative C(sp2)−C(sp3) bond formation. [ABSTRACT FROM AUTHOR]

We report the development of an electrocatalytic protocol for the chlorophosphinoylation of simple alkenes. Driven by electricity and mediated by a Mn catalyst, the heterodifunctionalization reaction takes place with high efficiency and regioselectivity. Cyclic voltammetry data are consistent with a mechanistic scenario based on anodically coupled electrolysis in which the generation of two distinct radical intermediates occur simultaneously on the anode and are both mediated by the Mn catalyst. [ABSTRACT FROM AUTHOR]