Electrochemical Dicarboxylation of Vinyl Epoxide with CO2 for the Facile and Selective Synthesis of Diacids

We present a novel electrochemical dicarboxylation of epoxides with CO2, characterized by the cleavage of two C–O single bonds. Not only are vinyl epoxides viable, but cyclic carbonates also serve as effective substrates, facilitating the synthesis of E‐configured adipic and octanedioic acids with high chemo‐, regio‐, and stereoselectivity. The synthetic practicality is further highlighted by the diverse functionalizations of the resulting multifunctional diacids. Mechanistic studies support the single‐electron transfer reduction of CO2 to its radical anion, which undergoes radical addition to the vinyl moiety of epoxides. The subsequent reductive cleavage of two C–O bonds, coupled with a nucleophilic attack on CO2, culminates in the formation of the desired diacid products.