Electrochemical Dehydration of Dicarboxylic Acids to Their Cyclic Anhydrides

Abstract An intramolecular electrochemical dehydration reaction of dicarboxylic acids to their cyclic anhydrides is presented. This electrolysis allows dicarboxylic acids as naturally abundant, inexpensive, safe, and readily available starting materials to be transformed into carboxylic anhydrides under mild reaction conditions. No conventional dehydration reagent is required. The obtained cyclic anhydrides are highly valuable reagents in organic synthesis, and in this report, we use them in‐situ for acylation reactions of amines to synthesize amides. This work is part of the recent progress in electrochemical dehydration, which – in contrast to electrochemical dehydrogenative reactions for example – is an underexplored field of research. The reaction mechanism was investigated by 18 O isotope labeling, revealing the formation of sulfate by electrochemical oxidation and hydrolysis of the thiocyanate‐supporting electrolyte. This transformation is not a classical Kolbe electrolysis, because it is non‐decarboxylative, and all carbon atoms of the carboxylic acid starting material are contained in the carboxylic anhydride. In total, 20 examples are shown with NMR yields up to 71 %.