Electrochemical Decarboxylative C-N Bond Formation

The carboxylic acids are featured with bench-stability, low cost, great structural diversity, non-toxicity and abundant commercial sources. Due to these remarkable properties, they are attractive synthetic feedstocks in the industrial landscape1. Recently, electrochemical approach has emerged as powerful tool in the decarboxylation reaction since it represents a mild and green strategy for the construction of new C-C and C-X (X= O, N) bonds obtaining CO2 and H2 as unique byproducts in the reaction2. The well-established Hofer-Moest reaction affords, after the double oxidation of the carboxylic acid, the formation of carbocation that could be intercept by a nucleophile to evolve in the desired product3. Based on this, our aim is to explore a novel electrochemical strategy starting from carboxylate anions for C-N bond formation. To the best of our knowledge, effective electrochemical methodologies which employ acetonitrile or other nitriles in this type of transformation are not reported yet. The transformation proceeds through the double oxidation mechanism where the carboxylate undergoes anodic oxidation to generate radical followed by another oxidation to afford carbocation which intercepted with nucleophile to obtained desire product. Notably, we observe the formation of unique and unreported intermediate when carboxylate substrates are treated with acetonitrile under electrochemical conditions. This intermediate suggests a key mechanistic role directing the pathway towards amines and amides. These findings provide the mechanistic approach and new insight into carboxylate-based amination and strategies through electrochemical activation. References: [1] L.C.Ji, Y.N.Lu, and S.Xia. Angew.Chem.Int. Ed., 2025, 64(9), p. e202423113. [2] C.Schotten, Green.Chem., 2020, 22(11), p. 3358-3375. [3] J. Xiang, M. Shang, Y. Kawamata1, H. Lundberg, S. H. Reisberg, M. Chen, P. Mykhailiuk, G. Beutner, M. R. C, A. Davies, M. Del Bel, G. M. Gallego, J. E. Spangler, J. Starr, S. Yang, D. G. Blackmond, P. S. Baran, Nature, 2019, 573, 398-403.