Electroreductive Dicarboxylation of Unactivated Skipped Dienes with CO2

Abstract Carboxylation of easily available alkenes with CO 2 is highly important to afford value‐added carboxylic acids. Although dicarboxylation of activated alkenes, especially 1,3‐dienes, has been widely investigated, the challenging dicarboxylation of unactivated 1, n ‐dienes ( n >3) with CO 2 remains unexplored. Herein, we report the first dicarboxylation of unactivated skipped dienes with CO 2 via electrochemistry, affording valuable dicarboxylic acids. Control experiments and DFT calculations support the single electron transfer (SET) reduction of CO 2 to its radical anion, which is followed by sluggish radical addition to unactivated alkenes, SET reduction of unstabilized alkyl radicals to carbanions and nucleophilic attack on CO 2 to give desired products. This reaction features mild reaction conditions, broad substrate scope, facile derivations of products and promising application in polymer chemistry.