Abstract
Nitrogen incorporation is fundamental in organic synthesis for functional materials, pharmaceuticals, and agrochemicals. While C–N bond formation has gained great progress, N-N bond construction remains challenging: existing methods rely on prefunctionalized precursors, and direct coupling is hindered by narrow substrate scope and poor reactivity control. Although transition-metal-catalyzed nitrene strategies exhibit high efficacy for intermolecular N–H insertion, nitrene-mediated N–N coupling under metal-free conditions has rarely been explored. Herein, we report a broadly applicable sulfilimine-based approach for selective N–N coupling. By leveraging sulfilimines as nitrene precursors, we achieve controlled release of highly reactive nitrene intermediates, enabling intermolecular N-N coupling with amines. This strategy provides an alternative pathway for nitrene-mediated N-H insertion reaction over conventional methods, providing a streamlined route for constructing complex N–N-containing architectures.
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Data availability
The authors declare that the data supporting the findings of this study are available within the paper and its supplementary information files. Experimental procedures, 1H NMR spectra, 13C NMR spectra, EPR spectra are available in the supplementary information. Source Data are provided with this paper. The X-ray crystallographic coordinates for the structures of compounds 53 and 70 reported in this study have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition numbers 2445166 and 2445167. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. All data are available from the corresponding author upon request. Source data are provided with this paper.
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Acknowledgements
We are grateful for the support of this work by the National Natural Science Foundation of China (22271254 to C.Y.L., 22401256 to M.Y., 22303062 to H.T., 22473014 to J.J., 21933005 to H.S.), the National Key R&D Program of China (2022YFA1505400 to J.J.), the Natural Science Foundation of Zhejiang province (LQN25B020003 to M.Y.) and Science Foundation of Zhejiang Sci-Tech University (ZSTU) (24262196-Y to M.Y.). We also acknowledge Q. Yang (Wuhan University) for assistance with electron paramagnetic resonance (EPR) experiments.
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C.Y.L. and M.Y. conceived the work. M.Y., J.F. and Z.F.X. designed the experiments and analysed the data. J.F., X.X. and Z.H.W. performed the synthetic experiments. X.W. and H.T. contributed to the DFT calculation. J.J. and H.S. designed and analysed mechanistic investigations using time-resolved spectroscopy. Y.H. performed time-resolved spectroscopy experiments. M.Y. and C.Y.L. described original manuscript and all authors revised.
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Yu, M., Feng, J., Wang, X. et al. Photo-induced selective N-N bond construction via harnessing nitrene release and transfer. Nat Commun (2026). https://doi.org/10.1038/s41467-026-68674-z
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DOI: https://doi.org/10.1038/s41467-026-68674-z
