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Electrochemically induced nickel catalysis for oxygenation reactions with water

Nature Catalysis volume 4, pages 116–123 (2021)Cite this article

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Abstract

Nickel has been found in some metalloproteins that execute catalytic aerobic oxygenation reactions in which nickel–dioxygen species are proposed as the key catalytic species. Thus, various nickel–dioxygen complexes have been prepared for biomimetic oxygenation reactions over the past 50 years, but they have often been used stoichiometrically rather than catalytically. The typical inertness of Ni(ii) complexes toward O2 poses a considerable challenge for their application in catalytic aerobic oxygenation. Here, we report a strategy to enable catalytic oxygenation with a simple Ni(ii)–bipyridine complex in which electrochemistry is employed to drive the cascade-activation process for the generation of both active Ni(ii)–peroxo species and O2 for the subsequent oxygenation reaction. We anticipate that this strategy will inspire the development of efficient nickel-catalysed aerobic oxygenations and promote the exploration of transition-metal-based oxidation chemistry in combination with electrochemistry.

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Fig. 1: Motivation and reaction development.
Fig. 2: Oxygenation of phosphine substrate and gram-scale synthesis experiment.
Fig. 3: Mechanistic studies.
Fig. 4: Proposed mechanism.

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Data availability

The data that support the findings of this study, including experimental procedures and compound characterization, are available in the online version of this paper in the accompanying Supplementary Information, or available from the authors upon reasonable request.

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Acknowledgements

Financial support from the National Natural Science Foundation of China (Nos. 21632001, 21772002 and 81821004), the Drug Innovation Major Project (2018ZX09711-001) and the Open Research Fund of the Shanghai Key Laboratory of Green Chemistry and Chemical Processes are greatly appreciated. We thank X.-Z. Wang and L.-Z. Wu at the Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, for instrumental help for the detection of H2. We also thank J. Peng in this group for reproducing the results of 2o and 2q.

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Authors and Affiliations

  1. State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Beijing, China

    Yujie Liang, Shi-Hui Shi, Rui Jin, Xu Qiu, Jialiang Wei, Hui Tan, Xue Jiang, Xiaomeng Shi, Song Song & Ning Jiao

  2. State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai, China

    Ning Jiao

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Contributions

Y.L. and N.J. conceived and designed the experiments; Y.L. carried out most experiments; S. Shi and R.J. carried out some control experiments; S. Shi reproduced the results of 2e and 2g; Y.L., S. Shi, R.J., X.Q., J.W., H.T., X.J., S. Song and N.J. analysed the data; X.S., Y.L. and N.J. analysed the ESI-HRMS data; Y.L. and N.J. wrote the manuscript; N.J. directed the project.

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Correspondence to Ning Jiao.

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The authors declare no competing interests.

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Peer review information Nature Catalysis thanks Markus Kärkäs and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–15, discussion, Table 1 and refs. 1–8.

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Liang, Y., Shi, SH., Jin, R. et al. Electrochemically induced nickel catalysis for oxygenation reactions with water. Nat Catal 4, 116–123 (2021). https://doi.org/10.1038/s41929-020-00559-w

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