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Photoinduced radical–ionic dihalogen transfer to carbon–carbon multiple bonds using oxime-based surrogates

Nature Synthesis volume 2, pages 439–447 (2023)Cite this article

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Abstract

Functional-group transfer strategies that utilize bench-stable and easy-to-handle surrogates create new synthetic avenues with the prospect to avoid the use of highly toxic and hazardous reagents. We disclose here an operationally simple and mechanistically distinct catalytic transfer protocol for the vicinal dihalogenation of carbon–carbon multiple bonds in alkenes, alkynes and allenes using easily synthesized oxime-based dihalogen surrogates. The reaction is promoted by visible-light photoredox catalysis. The success of this radical–ionic functional-group transfer hinges on the fragmentation of the surrogates into a halogen radical and halide anion with benzonitrile formation and sulfur dioxide evolution as the driving forces. Mechanistic studies suggest that oxidative quenching of the photocatalyst initiates the catalytic process. The released electrophilic halogen radical then engages in a radical addition to the carbon–carbon double or triple bond, followed by a radical–polar crossover and carbocation trapping by the previously formed halide anion to deliver the desired vicinal dihalides in a redox-neutral manner.

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Fig. 1: Transfer FG strategy.
Fig. 2: Development of radical–ionic transfer dichlorination of alkenes.
Fig. 3: Mechanistic investigations and proposed reaction mechanism.

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Data availability

The authors declare that all other data supporting the findings of this study are available within the article and Supplementary Information files, and also are available from the corresponding author upon request.

Change history

  • 20 March 2023

    In the version of this article initially published, “SO2” at the top right of the reaction arrow in Figure 3e originally appeared as “O2” and is now corrected in the HTML and PDF versions of the article.

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Acknowledgements

This research was supported by the Alexander von Humboldt Foundation (postdoctoral fellowship to M.Z., 2021‒2023), and J.Z. is grateful for a Shenzhen Postdoctoral Scholarship (2021‒2023). M.O. is indebted to the Einstein Foundation Berlin for an endowed professorship. We thank members of the laboratory of Matthias Drieß (TU Berlin) for their competent assistance with operando ultraviolet–visible and cyclic voltammetry measurements.

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  1. These authors contributed equally: Muliang Zhang, Jinghui Zhang.

Authors and Affiliations

  1. Institut für Chemie, Technische Universität Berlin, Berlin, Germany

    Muliang Zhang, Jinghui Zhang & Martin Oestreich

  2. International Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen, China

    Jinghui Zhang

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  1. Muliang Zhang
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Contributions

M.Z. and M.O. conceived and designed the experiments. M.Z. and J.Z. performed the experiments and analysed the data. M.Z., J.Z. and M.O. discussed the results and co-wrote the paper.

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Correspondence to Martin Oestreich.

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Nature Synthesis thanks Xiaobing Wan, Peng-Ju Xia 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 1–9 and Figs. 1–211.

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Zhang, M., Zhang, J. & Oestreich, M. Photoinduced radical–ionic dihalogen transfer to carbon–carbon multiple bonds using oxime-based surrogates. Nat. Synth 2, 439–447 (2023). https://doi.org/10.1038/s44160-023-00256-z

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