Abstract Carboxylation of easily available alkenes with CO2 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 CO2 remains unexplored. Herein, we report the first dicarboxylation of unactivated skipped dienes with CO2 via electrochemistry, affording valuable dicarboxylic acids. Control experiments and DFT calculations support the single electron transfer (SET) reduction of CO2 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 CO2 to give desired products. This reaction features mild reaction conditions, broad substrate scope, facile derivations of products and promising application in polymer chemistry.
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