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Electrochemically Catalyzed Newman–Kwart Rearrangement: Mechanism, Structure–Reactivity Relationship, and Parallels to Photoredox Catalysis

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    Article

    Electrochemically Catalyzed Newman–Kwart Rearrangement: Mechanism, Structure–Reactivity Relationship, and Parallels to Photoredox Catalysis
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    • Arend F. Roesel
      Arend F. Roesel
      Institute of Chemistry, Rostock University, Albert-Einstein-Str. 3a, 18059 Rostock, Germany
      More by Arend F. Roesel
    • Mihkel Ugandi
      Mihkel Ugandi
      Chair for Theoretical Chemistry, Ruhr-University Bochum, 44780 Bochum, Germany
      More by Mihkel Ugandi
    • Nguyen Thi Thu Huyen
      Nguyen Thi Thu Huyen
      Institute of Chemistry, Rostock University, Albert-Einstein-Str. 3a, 18059 Rostock, Germany
      School of Chemical Engineering, Hanoi University of Science and Technology, 1 Dai Co Viet Road, Hanoi, Vietnam
      More by Nguyen Thi Thu Huyen
    • Michal Májek
      Michal Májek
      Institute of Chemistry, Rostock University, Albert-Einstein-Str. 3a, 18059 Rostock, Germany
      Department of Organic Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, Mlynská Dolina, Ilkovičova 6, 84215 Bratislava, Slovakia
      More by Michal Májek
    • Timo Broese
      Timo Broese
      Institute of Chemistry, Rostock University, Albert-Einstein-Str. 3a, 18059 Rostock, Germany
      More by Timo Broese
    • Michael Roemelt*
      Michael Roemelt
      Chair for Theoretical Chemistry, Ruhr-University Bochum, 44780 Bochum, Germany
      *Email: [email protected]
      More by Michael Roemelt
      Orcidhttp://orcid.org/0000-0002-4780-5354
    • Robert Francke*
      Robert Francke
      Institute of Chemistry, Rostock University, Albert-Einstein-Str. 3a, 18059 Rostock, Germany
      *Email: [email protected]
      More by Robert Francke
      Orcidhttp://orcid.org/0000-0002-4998-1829
    Other Access OptionsSupporting Information (1)

    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2020, 85, 12, 8029–8044
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.joc.0c00831
    Published May 26, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    The facilitation of redox-neutral reactions by electrochemical injection of holes and electrons, also known as “electrochemical catalysis”, is a little explored approach that has the potential to expand the scope of electrosynthesis immensely. To systematically improve existing protocols and to pave the way toward new developments, a better understanding of the underlying principles is crucial. In this context, we have studied the Newman–Kwart rearrangement of O-arylthiocarbamates to the corresponding S-aryl derivatives, the key step in the synthesis of thiophenols from the corresponding phenols. This transformation is a particularly useful example because the conventional method requires temperatures up to 300 °C, whereas electrochemical catalysis facilitates the reaction at room temperature. A combined experimental–quantum chemical approach revealed several reaction channels and rendered an explanation for the relationship between the structure and reactivity. Furthermore, it is shown how rapid cyclic voltammetry measurements can serve as a tool to predict the feasibility for specific substrates. The study also revealed distinct parallels to photoredox-catalyzed reactions, in which back-electron transfer and chain propagation are competing pathways.

    Copyright © 2020 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.joc.0c00831.

    • Electrochemical data, cartesian coordinates of calculated molecules, and NMR spectra (PDF)

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    Cited By

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    This article is cited by 22 publications.

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    2. Yunyun Liu, Leiling Deng, Haijin Guo, Jie-Ping Wan. Annulative Nonaromatic Newman–Kwart-Type Rearrangement for the Synthesis of Sulfur Heteroaryls. Organic Letters 2024, 26 (1) , 46-50. https://doi.org/10.1021/acs.orglett.3c03581
    3. Linkun Ying, Yao Chen, Xiangrui Song, Zengqiang Song. Metal-Free Thiocarbamation of Quinolinones: Direct Access to 3,4-Difunctionalized Quinolines and Quinolinonyl Thiocarbamates at Room Temperature. The Journal of Organic Chemistry 2023, 88 (19) , 13894-13907. https://doi.org/10.1021/acs.joc.3c01504
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    5. Nicholas E. S. Tay, Dan Lehnherr, Tomislav Rovis. Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis. Chemical Reviews 2022, 122 (2) , 2487-2649. https://doi.org/10.1021/acs.chemrev.1c00384
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    7. J. M. Coxon. Molecular Rearrangements. 2024, 433-505. https://doi.org/10.1002/9781119716846.ch11
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    11. Prakash Kumar Sahoo, Yu Zhang, Yuman Qin, Peng Ren, Robin Cauwenbergh, Gandhi Siva Raman, Shoubhik Das. Robust late-stage benzylic C(sp3)–H aminations by using transition metal-free photoredox catalysis. Journal of Catalysis 2023, 425 , 80-88. https://doi.org/10.1016/j.jcat.2023.06.002
    12. Robert Francke, R. Daniel Little. Electrochemical catalysis of redox-neutral organic reactions. Current Opinion in Electrochemistry 2023, 40 , 101315. https://doi.org/10.1016/j.coelec.2023.101315
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    17. Jiaoyan Zhao, Hongyan Yuan, Ruonan Chen, Hongyu Chen, Yanhua Zhang. Electrochemical Catalytic Hydrocarbonylation of Arylacetylenes. Asian Journal of Organic Chemistry 2022, 11 (2) https://doi.org/10.1002/ajoc.202100681
    18. Mitra Sanie, Ehsan Zahedi, Seyed Hosein Ghorbani, Ahmad Seif. Insights into the kinetics and molecular mechanism of the Newman–Kwart rearrangement. New Journal of Chemistry 2021, 45 (36) , 16978-16988. https://doi.org/10.1039/D1NJ02966E
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    22. Kaii Nakayama, Hidehiro Kamiya, Yohei Okada. EC-Backward-E Electrochemistry in Radical Cation Diels-Alder Reactions. Journal of The Electrochemical Society 2020, 167 (15) , 155518. https://doi.org/10.1149/1945-7111/abb97f
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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2020, 85, 12, 8029–8044
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.joc.0c00831
    Published May 26, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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