Abstract
Reductive amination of renewable biomass is a key pathway for producing high-value N-containing chemicals. The reductive amination of biomass-derived furfural to synthesize ethyl-2-furylmethylamine (EFYA) using waste acetonitrile (MeCN) as the N source is a promising valorization approach. Compared with thermal catalysis, electrocatalysis offers a greener method for EFYA synthesis. However, efficient electrochemical C–N coupling is challenging due to furfural’s higher reactivity than MeCN. Here we report an electrocatalytic EFYA synthesis with a 98% yield on Fe–CuOx by stabilizing Cu2+ to reverse the reduction sequence of furfural and MeCN. Cu2+ enhances MeCN adsorption and promotes its reduction while inhibiting furfural’s electrochemical reduction side reaction. Stable EFYA production is achieved by doping Fe3+ through cycling of the Fe3+/Fe2+ redox pair to maintain the continuous activity of the reactive Cu2+ species. This strategy is extended to synthesize secondary amines from other aldehydes and nitriles. This work presents a general strategy for efficient electrochemical C–N coupling to synthesize secondary amines, inspiring further applications of biomass-derived molecules.
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Acknowledgements
This work was supported by the National Key R&D Program of China (grant no. 2023YFA1507400 (Y.Z.)), the National Natural Science Foundation of China (grant nos. 22425021 (S.W.) and U24A20498 (Y.Z.)) and the Science and Technology Innovation Program of Hunan Province (grant no. 2025RC1038 (Y.Z.)). We thank the Analytical Instrumentation Center of Hunan University for assistance with NMR and Raman measurements.
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S.W. and Y.Z. were responsible for designing and coordinating the entire project. Y.P. and R.M. completed the work related to electrochemical experiments. Q.L. and Q.A. performed the testing and analysis of SR-FTIR spectroscopy. C.-L.D. and T.T.T.N. completed the testing and analysis of synchrotron radiation absorption spectra for the samples. Y.J., T.X., T.L., C.M. and Y.Y. jointly performed the theoretical calculations. Z. Xiao and D.X. completed the separation and purification of the products. Y.F., Z. Xia and Y.H. assisted in data processing and mechanism elucidation. Y.P. wrote the paper with the participation of all authors. All authors discussed the results in detail and commented on the paper.
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Pan, Y., Jing, Y., Xu, T. et al. Reversing the reduction sequence of aldehydes and nitriles for electrochemical C–N coupling. Nat. Synth (2026). https://doi.org/10.1038/s44160-026-01036-1
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DOI: https://doi.org/10.1038/s44160-026-01036-1
