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Photoelectrocatalytic arene C–H amination

Nature Catalysis volume 2, pages 366–373 (2019)Cite this article

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Abstract

Photoelectrochemical cells are widely studied for solar energy conversion. However, they have rarely been used for the synthesis of high added-value organic molecules. Here we describe a strategy to use haematite, an abundant and robust photoanode, for non-directed arene C–H amination. Under illumination, the photogenerated holes in haematite oxidize electron-rich arenes to radical cations, which further react with azoles to give nitrogen heterocycles of medicinal interest. Unusual ortho selectivity was achieved, probably due to a hydrogen-bonding interaction between the substrates and the hexafluoroisopropanol co-solvent. The method exhibits broad scope and is successfully applied for the late-stage functionalization of several pharmaceutical molecules.

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Fig. 1: PEC cells.
Fig. 2: Arene C–H amination.
Fig. 3: Late-stage functionalization of pharmaceuticals.
Fig. 4: (Photo)electrochemical measurements.
Fig. 5: Mechanistic hypothesis.

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Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

This work was supported by the EPFL, a consolidator grant from the European Research Council under the European Union’s Horizon 2020 research and innovation programme (no. 681292 to X.H.), the PECHouse3 project from the Swiss Federal Office of Energy (no. SI/500090-03, M.G. and J.L.), the Strategic Japanese–Swiss Science and Technology Programme from the Swiss National Science Foundation (no. 514259, M.G. and J.L.) and the Chinese Thousand Talents Program for Young Professionals (J.L.).

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Authors and Affiliations

  1. Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), ISIC-LSCI, Lausanne, Switzerland

    Lei Zhang, Laurent Liardet & Xile Hu

  2. Laboratory of Photonics and Interfaces, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), ISIC-LPI, Lausanne, Switzerland

    Jingshan Luo, Dan Ren & Michael Grätzel

  3. Institute of Photoelectronic Thin Film Devices and Technology, College of Electronic Information and Optical Engineering, Nankai University, Tianjin, China

    Jingshan Luo

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Contributions

X.H. directed the project. L.Z. conceived and performed most of experiments. L.L. prepared the haematites and conducted the EIS analysis. J.L. and D.R. measured the IPCE. X.H. and L.Z. wrote the paper, with input from others. All the authors analysed the results and reviewed the paper.

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Correspondence to Xile Hu.

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Supplementary Methods, Supplementary References, Supplementary Figures 1–6

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Zhang, L., Liardet, L., Luo, J. et al. Photoelectrocatalytic arene C–H amination. Nat Catal 2, 366–373 (2019). https://doi.org/10.1038/s41929-019-0231-9

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