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Comprehensive Mechanistic Scenario for the Cu-Mediated Asymmetric Propargylic Sulfonylation Forging Tertiary Carbon Stereocenters

  • Aleria Garcia-Roca
    Aleria Garcia-Roca
    Institute of Chemical Research of Catalonia (ICIQ), the Barcelona Institute of Science and Technology (BIST), Av. Països Catalans 16, 43007 Tarragona, Spain
    Departament de Química Física i Inorgánica, Universitat Rovira i Virgili, Marcel·lí Domingo s/n, 43007 Tarragona, Spain
  • Raúl Pérez-Soto
    Raúl Pérez-Soto
    Institute of Chemical Research of Catalonia (ICIQ), the Barcelona Institute of Science and Technology (BIST), Av. Països Catalans 16, 43007 Tarragona, Spain
    Departament de Química Física i Inorgánica, Universitat Rovira i Virgili, Marcel·lí Domingo s/n, 43007 Tarragona, Spain
  • Georgiana Stoica
    Georgiana Stoica
    Institute of Chemical Research of Catalonia (ICIQ), the Barcelona Institute of Science and Technology (BIST), Av. Països Catalans 16, 43007 Tarragona, Spain
  • Jordi Benet-Buchholz
    Jordi Benet-Buchholz
    Institute of Chemical Research of Catalonia (ICIQ), the Barcelona Institute of Science and Technology (BIST), Av. Països Catalans 16, 43007 Tarragona, Spain
  • Feliu Maseras*
    Feliu Maseras
    Institute of Chemical Research of Catalonia (ICIQ), the Barcelona Institute of Science and Technology (BIST), Av. Països Catalans 16, 43007 Tarragona, Spain
    *Email: [email protected]
  • , and 
  • Arjan W. Kleij*
    Arjan W. Kleij
    Institute of Chemical Research of Catalonia (ICIQ), the Barcelona Institute of Science and Technology (BIST), Av. Països Catalans 16, 43007 Tarragona, Spain
    Catalan Institute of Research and Advanced Studies (ICREA), Pg. Lluïs Companys 23, 08010 Barcelona, Spain
    *Email: [email protected]
Cite this: J. Am. Chem. Soc. 2023, 145, 11, 6442–6452
Publication Date (Web):March 8, 2023
https://doi.org/10.1021/jacs.3c00188
Copyright © 2023 American Chemical Society

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    Abstract

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    Metal-catalyzed propargylic transformations represent a powerful tool in organic synthesis to achieve new carbon–carbon and carbon–heteroatom bonds. However, detailed knowledge about the mechanistic intricacies related to the asymmetric formation of propargylic products featuring challenging heteroatom-substituted tertiary stereocenters is scarce and therefore provides an inspiring challenge. Here, we present a meticulous mechanistic analysis of a propargylic sulfonylation reaction promoted by a chiral Cu catalyst through a combination of experimental techniques and computational studies. Surprisingly, the enantio-discriminating step is not the coupling between the nucleophile and the propargylic precursor but rather the following proto-demetalation step, a scenario further validated by computing enantio-induction levels under other previously reported experimental conditions. A full mechanistic scenario for this propargylic substitution reaction is provided, including a catalyst pre-activation stage, a productive catalytic cycle, and an unanticipated non-linear effect at the Cu(I) oxidation level.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.3c00188.

    • Experimental and analytical procedures, characterization of all new and relevant known compounds, computational details, additional free-energy profiles, and Cartesian coordinates of calculated structures (PDF)

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    CCDC 21681952168201 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cited By

    This article is cited by 5 publications.

    1. Ruinan Zhao, Shuang Deng, Rongkang Huang, Han-Han Kong, Yuepeng Lu, Tingrui Yin, Jiaqiang Wang, Ying Li, Cuiju Zhu, Fangfang Pan, Xiaotian Qi, Hao Xu. Enantioselective Copper-Catalyzed Dearomative Spiroannulation of β-Naphthols or Indoles with Yne-Allylic Esters. ACS Catalysis 2024, Article ASAP.
    2. Guiqin Li, Yahui Li, Peidong Sun, Jingwen Huang, Tongyu Xu, Fanlong Zeng, Xiang-Ping Hu. Copper-Catalyzed Difunctionalization of Propargylic Carbonates through Tandem Nucleophilic Substitution/Boroprotonation. Organic Letters 2024, 26 (21) , 4443-4450. https://doi.org/10.1021/acs.orglett.4c01080
    3. Debasish Ghorai, Balázs L. Tóth, Matteo Lanzi, Arjan W. Kleij. Vinyl and Alkynyl Substituted Heterocycles as Privileged Scaffolds in Transition Metal Promoted Stereoselective Synthesis. Accounts of Chemical Research 2024, 57 (5) , 726-738. https://doi.org/10.1021/acs.accounts.3c00760
    4. Chunming Gui, Yuanyuan Peng, Yang Zhou, Yixuan Zheng, Haifeng Wang, Qiongjiao Yan, Hui Zhou, Wei Wang, Fen-Er Chen. Cu-Catalyzed Intermolecular Asymmetric Propargylic Substitution of N-Hydroxyphthalimide Esters with Propargyl Carbonates. ACS Catalysis 2023, 13 (20) , 13735-13742. https://doi.org/10.1021/acscatal.3c03814
    5. Zi-Qi Geng, Chunhui Zhao, Hao-Dong Qian, Si-Jia Li, Hao Peng, Hao Xu. Cu/Ag-Mediated One-Pot Enantioselective Synthesis of Fully Decorated 1,2,3-Triazolo[1,5-a]pyrazines. Organic Letters 2023, 25 (24) , 4504-4509. https://doi.org/10.1021/acs.orglett.3c01524