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Asymmetric-waveform alternating current-promoted silver catalysis for C–H phosphorylation

Nature Synthesis volume 2, pages 172–181 (2023)Cite this article

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Abstract

Preventing metal deposition by cathodic reduction is a formidable challenge during transition-metal-catalysed electrosynthesis under direct current (d.c.) electrolysis conditions, especially for noble metal catalysis. To overcome the limitation of reductive metal deposition, we now report an asymmetric-waveform alternating current (a.c.) electrolysis protocol for silver-catalysed C–H phosphorylation, where our a.c.-based approach achieves smooth regeneration of the silver catalyst. A wide variety of alkynes, alkenes and (hetero)arenes are reactive under our a.c. electrolysis conditions, delivering the desired phosphite ester derivatives (88 examples) in good yields, whereas these products are often obtained in poor yields under d.c. electrolysis conditions. Notably, this protocol can be expanded to Pd- and Cu-catalysed C–H functionalization. This electrochemical metal-catalysis strategy is distinct from traditional d.c. electrosynthesis and has great potential to be used in the fine organic chemical industry.

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Fig. 1: Electrosynthetic strategies for transition-metal-catalysed C–H/X–H cross-coupling.
Fig. 2: The mechanistic studies and proposed reaction mechanism.
Fig. 3: Substrate scopes for a.c. electrosynthesis of alkynes and alkenes.
Fig. 4: Substrate scopes for a.c. electrosynthesis of (hetero)arenes and synthetic applications.

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All data that support the findings of this study, which include device construction, experimental procedures and compound characterization, are available within the manuscript and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Key R&D Program of China (grant no. 2021YFA1500104, to A.L.), National Natural Science Foundation of China (grant no. 22031008, to A.L.), the Science Foundation of Wuhan (grant no. 2020010601012192, to A.L.) and the China Postdoctoral Science Foundation (grant nos. 2021M702520 and BX2021225, to L.Z.). We thank S. Tang from Shanghai Jiao Tong University and A. D. Chowdhury from Wuhan University for advising on the manuscript.

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  1. These authors contributed equally: Li Zeng, Ying Jiao, Weishun Yan.

Authors and Affiliations

  1. College of Chemistry and Molecular Sciences, Institute for Advanced Studies, Wuhan University, Wuhan, P. R. China

    Li Zeng, Ying Jiao, Weishun Yan, Yong Wu, Shengchun Wang, Pengjie Wang, Dan Wang, Qinghong Yang, Jianxing Wang, Heng Zhang & Aiwen Lei

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Contributions

A.L. and L.Z. contributed to the conception and design of the experiments. Y.J., W.Y., Y.W., S.W., P.W., D.W., Q.Y., J.W. and H.Z. performed the experiments. L.Z. and A.L. cowrote the manuscript and all authors contributed to data analysis and scientific discussion. L.Z., Y.J. and W.Y. contributed equally to this work.

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Correspondence to Aiwen Lei.

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Nature Synthesis thanks Long Luo and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Peter Seavill, in collaboration with the Nature Synthesis team.

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Experimental details, Supplementary Sections 1–13, Figs. 1–41 and Tables 1–8.

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Unprocessed atomic absorption spectrum data (Fig. 2c,d,e,f,i) and current data (Fig. 2h).

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Zeng, L., Jiao, Y., Yan, W. et al. Asymmetric-waveform alternating current-promoted silver catalysis for C–H phosphorylation. Nat. Synth 2, 172–181 (2023). https://doi.org/10.1038/s44160-022-00197-z

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