Abstract
Photoinduced transition metal catalysis offers innovative strategies for fostering novel chemical reactions and improving established ones. In this work, we present a highly efficient, photoinduced Mn(II)-bipyridine catalyzed C–N, C-O and C-S coupling reaction between aryl halides—particularly less reactive aryl chlorides—and nucleophiles containing nitrogen, oxygen, and sulfur. This protocol does not need an external photocatalyst, as the single Mn(II)–bipyridine complex simultaneously serves as both the light-harvester and the metal catalyst. This method exhibits excellent substrate scope, covering eight different nitrogen sources for C-N coupling, as well as C-O coupling with alcohols, C-S coupling with thiophenols, encompassing more than 150 examples, with yields reaching up to 94%. Mechanistic studies suggest that this reaction may be initiated and sustained by the Mn(I) species through the photoinduced homolysis of the catalyst precursor bipyridine-Mn(II)(OAc)2, likely proceeding via a Mn(I)/Mn(III) catalytic cycle.
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Data availability
Data available in this study are provided in the supplementary information. Crystallographic data coordinates for structures reported in this article has been deposited at the Cambridge Crystallographic Data Center (CCDC), under deposition numbers CCDC 2224253 (Mn complex 174). The sedata can be obtained free of charge from the Cambridge Crystallographic Data Center via https://www.ccdc.cam.ac.uk/structures/.
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Acknowledgements
This research is supported by the National Natural Science Foundation of China (Grant No. 22171174, 22471150 to D.X.; Grant No. 22402113 to G.S.), the Fundamental Research Funds for the Central Universities (Grant No. GK202406026 to T.K.; Grant No. GK202505023 to G.S.; Grant No. GK202505026 to D.X.), the Innovation Capability Support Program of Shaanxi (Grant No. 2023-CX-TD-28 to D.X.), the Fundamental Science Research Project of Shaanxi for Chemistry, Biology (Grant No. 22JHZ0027 to D.X.), the Natural Science Foundation of Shaanxi Province (Grant No. 2024JC-YBQN-0075 to G.S.; Grant No. 2025JC-YBQN-144 to T.K.), the State Key Laboratory of Natural and Biomimetic Drugs (Grant No. K202437 to G.S.), the Key Research and Development Program of Shaanxi (Grant No. 2024CY-JJQ-26 to D.X.), and the S&T Program of Energy Shaanxi Laboratory (Grant No. ESLB202420 00 to D.X.).
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D.X. conceived and directed the project. G.S. designed and conducted experiments, analyzed data. J.S. participated in the substrate scope expansion. Q.L., X.S., X.L., D.P., J.F., and H.S. helped analyzed data. T.K., J.D., G.L., and C.W. contributed to the project discussion. G.S. prepared the manuscript. D.X. wrote the manuscript. All authors discussed the experimental results and commented on the manuscript.
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Song, G., Song, J., Li, Q. et al. Photoinduced Mn catalysis for efficient platform for C-heteroatom bond coupling of aryl halides. Nat Commun (2026). https://doi.org/10.1038/s41467-026-70925-y
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DOI: https://doi.org/10.1038/s41467-026-70925-y
