ACS Publications. Most Trusted. Most Cited. Most Read
Supporting-Electrolyte-Free Anodic Oxidation of Oxamic Acids into Isocyanates: An Expedient Way to Access Ureas, Carbamates, and Thiocarbamates

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Org. Process Res. Dev. 2021, 25, 12, 2614-2621
    Article

    Supporting-Electrolyte-Free Anodic Oxidation of Oxamic Acids into Isocyanates: An Expedient Way to Access Ureas, Carbamates, and Thiocarbamates
    Click to copy article linkArticle link copied!

    Other Access OptionsSupporting Information (1)

    Organic Process Research & Development

    Cite this: Org. Process Res. Dev. 2021, 25, 12, 2614–2621
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.oprd.1c00112
    Published May 20, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    We report a new electrochemical supporting-electrolyte-free method for synthesizing ureas, carbamates, and thiocarbamates via the oxidation of oxamic acids. This simple, practical, and phosgene-free route includes the generation of an isocyanate intermediate in situ via anodic decarboxylation of an oxamic acid in the presence of an organic base, followed by the one-pot addition of suitable nucleophiles to afford the corresponding ureas, carbamates, and thiocarbamates. This procedure is applicable to different amines, alcohols, and thiols. Furthermore, when single-pass continuous electrochemical flow conditions were used and this reaction was run in a carbon graphite Cgr/Cgr flow cell, urea compounds could be obtained in high yields within a residence time of 6 min, unlocking access to substrates that were inaccessible under batch conditions while being easily scalable.

    Copyright © 2021 American Chemical Society

    Subjects

    what are subjects

    Keywords

    what are keywords

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.oprd.1c00112.

    • Experimental details and procedures, including copies of NMR spectra (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 22 publications.

    1. Chunhua Ma, Qing Guo, Hui Meng, Shengnan Yan, Qingjie Ding, Yuqin Jiang, Bing Yu. Photoredox-Catalyzed Carbamoyl Radical-Initiated Dearomative Spirocyclization To Access Spiro-Cyclohexadiene Oxindoles. Organic Letters 2024, 26 (40) , 8503-8508. https://doi.org/10.1021/acs.orglett.4c03045
    2. Feba Pulikkottil, John S. Burnett, Jérémy Saiter, Charles A. I. Goodall, Bini Claringbold, Kevin Lam. eFluorination for the Rapid Synthesis of Carbamoyl Fluorides from Oxamic Acids. Organic Letters 2024, 26 (29) , 6103-6108. https://doi.org/10.1021/acs.orglett.4c01605
    3. Dan Lehnherr, Longrui Chen. Overview of Recent Scale-Ups in Organic Electrosynthesis (2000–2023). Organic Process Research & Development 2024, 28 (2) , 338-366. https://doi.org/10.1021/acs.oprd.3c00340
    4. David T. Mooney, Benjamin D. T. Donkin, Nemrud Demirel, Peter R. Moore, Ai-Lan Lee. Direct C–H Functionalization of Phenanthrolines: Metal- and Light-Free Dicarbamoylations. The Journal of Organic Chemistry 2021, 86 (23) , 17282-17293. https://doi.org/10.1021/acs.joc.1c02425
    5. Cuihan Zhou, Dushyant Singh, Bruce A. Arndtsen. A Versatile Carbonylative Approach to Ureas and Carbamates through Light Activated Nickel Catalyzed Formation of Aliphatic Isocyanates. Angewandte Chemie 2025, 137 (17) https://doi.org/10.1002/ange.202423519
    6. Cuihan Zhou, Dushyant Singh, Bruce A. Arndtsen. A Versatile Carbonylative Approach to Ureas and Carbamates through Light Activated Nickel Catalyzed Formation of Aliphatic Isocyanates. Angewandte Chemie International Edition 2025, 64 (17) https://doi.org/10.1002/anie.202423519
    7. Yuyu Dai, Wei Niu, Jiapeng Huang, Jiarui Sun, Xiangsheng Xu. Photo-induced amidation/Smiles rearrangement of alkenes for synthesizing quaternary-carbon-containing succinyldiamides. Organic & Biomolecular Chemistry 2025, 23 (6) , 1330-1337. https://doi.org/10.1039/D4OB01863J
    8. Ru‐Han A, Yong‐Wang Huo, Xiao‐Feng Wu. Silver‐Catalyzed Decarboxylative Coupling of Oxamic Acids with Styrenes to Synthesize E ‐Cinnamamides: A Distinguish Reaction Pathway. ChemistryOpen 2025, 22 https://doi.org/10.1002/open.202400513
    9. Wei Niu, Yanlong Liu, Erling Dai, Jiarui Sun, Yuyu Dai, Xiangsheng Xu. Synthesis of amide-functionalized isoquinoline derivatives by photo-induced carbamoyl radical cascade amidation/cyclization. Organic & Biomolecular Chemistry 2025, 54 https://doi.org/10.1039/D5OB00465A
    10. Margaux Badufle, Frédéric Robert, Yannick Landais. Copper‐Mediated Synthesis of N ‐Aryl‐Oxamic Acids. Chemistry – A European Journal 2024, 30 (57) https://doi.org/10.1002/chem.202402298
    11. Yingbin Gong, Leilei Yan, Zhiqiang Guo. Na 2 CO 3 -promoted synthesis of thiocarbamates from isocyanates and thiols under mild conditions. Organic & Biomolecular Chemistry 2024, 22 (31) , 6277-6281. https://doi.org/10.1039/D4OB01068J
    12. Lilla G. Gombos, Joachim Nikl, Siegfried R. Waldvogel. Dual Roles of Supporting Electrolytes in Organic Electrosynthesis. ChemElectroChem 2024, 11 (8) https://doi.org/10.1002/celc.202300730
    13. Michał Michalak, Paweł Czerwiński, Katarzyna Śniady‐Maciążek, Szymon Musioł, Oksana Danylyuk, Michał Wierzbicki, Michele Tomasini, Albert Poater. Chiral NHC Ligands for Enantioselective Gold(I) Catalysis Under Aerobic Conditions: the Importance of Conformational Flexibility and Steric Hindrance of NHC Ligand on Reactivity. Chemistry – A European Journal 2024, 30 (13) https://doi.org/10.1002/chem.202303241
    14. Gülbin Kurtay, Jonathan Lusseau, Frédéric Robert, Yannick Landais. Iron-Catalyzed Oxidative Decarboxylation of Oxamic Acids: A Safe and Efficient Photochemical Route to Urethanes. Synlett 2024, 35 (03) , 342-346. https://doi.org/10.1055/a-2131-3368
    15. Ajijur Rahaman, Shivani Singh Chauhan, Sukalyan Bhadra. Recent advances in catalytic decarboxylative transformations of carboxylic acid groups attached to a non-aromatic sp 2 or sp carbon. Organic & Biomolecular Chemistry 2023, 21 (28) , 5691-5724. https://doi.org/10.1039/D3OB00682D
    16. Muzhao Wang, Paul Wilson. An electrochemical Hofmann rearrangement on acrylamide copolymers. Polymer Chemistry 2023, 14 (26) , 3057-3062. https://doi.org/10.1039/D3PY00594A
    17. Ikechukwu Martin Ogbu, Gülbin Kurtay, Margaux Badufle, Frédéric Robert, Carlos Silva Lopez, Yannick Landais. PIDA‐mediated Oxidative Decarboxylation of Oxamic Acids. The Role of Radical Acidity Enhancement.. Chemistry – A European Journal 2023, 29 (15) https://doi.org/10.1002/chem.202202963
    18. Kevin Lam. Electrosynthesis: A Practical Way to Access Highly Reactive Intermediates. Synlett 2022, 33 (20) , 1953-1960. https://doi.org/10.1055/a-1890-9162
    19. Ikechukwu Martin Ogbu, Gülbin Kurtay, Frédéric Robert, Yannick Landais. Oxamic acids: useful precursors of carbamoyl radicals. Chemical Communications 2022, 58 (55) , 7593-7607. https://doi.org/10.1039/D2CC01953A
    20. Makoto Ito, Kaishi Hori, Kazuki Maeda, Ken-ichi Yakigaya, Nobuyuki Uematsu, Naoki Matsuoka. Optimized synthesis of cyclic fluorinated sulfonylimide lithium salts to suppress aluminum corrosion in lithium-ion batteries. Journal of Fluorine Chemistry 2022, 257-258 , 109975. https://doi.org/10.1016/j.jfluchem.2022.109975
    21. Alessia Petti, Kevin Lam. Recent Advances in the Kolbe and Non-Kolbe Electrolysis of Carboxylic Acids. 2022, 29-59. https://doi.org/10.1039/9781839164828-00029
    22. Svetlana O. Kasatkina, Kirill K. Geyl, Sergey V. Baykov, Mikhail S. Novikov, Vadim P. Boyarskiy. “Urea to Urea” Approach: Access to Unsymmetrical Ureas Bearing Pyridyl Substituents. Advanced Synthesis & Catalysis 2022, 364 (7) , 1295-1304. https://doi.org/10.1002/adsc.202101490
    Download PDF
    Go to Organic Process Research & Development
    Get e-Alerts
    Get e-Alerts

    Organic Process Research & Development

    Cite this: Org. Process Res. Dev. 2021, 25, 12, 2614–2621
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.oprd.1c00112
    Published May 20, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

    Article Views

    3911

    Altmetric

    -

    Citations

    22
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.