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.
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Electrochemical Dicarboxylation of Vinyl Epoxide with CO2 for the Facile and Selective Synthesis of Diacids.
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East China Normal University, School of Chemistry and Molecular Engineering, 3663 N. Zhongshan Rd., 200062, Shanghai, CHINA.
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