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Enantioselective Synthesis of Nitrogen–Nitrogen Biaryl Atropisomers via Copper-Catalyzed Friedel–Crafts Alkylation Reaction

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    Enantioselective Synthesis of Nitrogen–Nitrogen Biaryl Atropisomers via Copper-Catalyzed Friedel–Crafts Alkylation Reaction
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    • Xiao-Mei Wang
      Xiao-Mei Wang
      College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, Shandong 266071, China
      More by Xiao-Mei Wang
    • Peng Zhang
      Peng Zhang
      College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, Shandong 266071, China
      More by Peng Zhang
    • Qi Xu
      Qi Xu
      College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, Shandong 266071, China
      More by Qi Xu
    • Chang-Qiu Guo
      Chang-Qiu Guo
      College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, Shandong 266071, China
      More by Chang-Qiu Guo
    • De-Bing Zhang
      De-Bing Zhang
      College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, Shandong 266071, China
      More by De-Bing Zhang
    • Chuan-Jun Lu*
      Chuan-Jun Lu
      College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, Shandong 266071, China
      *[email protected]
      More by Chuan-Jun Lu
    • Ren-Rong Liu*
      Ren-Rong Liu
      College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, Shandong 266071, China
      *[email protected]
      More by Ren-Rong Liu
      Orcidhttps://orcid.org/0000-0002-6474-3909
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    Cite this: J. Am. Chem. Soc. 2021, 143, 37, 15005–15010
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    https://doi.org/10.1021/jacs.1c07741
    Published September 8, 2021
    Copyright © 2021 American Chemical Society
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    Abstract

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    Nitrogen–nitrogen bonds containing motifs are ubiquitous in natural products and bioactive compounds. However, the atropisomerism arising from a restricted rotation around an N–N bond is largely overlooked. Here, we describe a method to access the first enantioselective synthesis of N–N biaryl atropisomers via a Cu-bisoxazoline-catalyzed Friedel–Crafts alkylation reaction. A wide range of axially chiral N–N bisazaheterocycle compounds were efficiently prepared in high yields with excellent enantioselectivities via desymmetrization and kinetic resolution. Heating experiments showed that the axially chiral bisazaheterocycle products have high rotational barriers.

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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/jacs.1c07741.

    • Experimental procedures, additional figures and tables, compound characterization data and NMR spectra, and chiral HPLC chromatograms (PDF)

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    CCDC 2097670 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 CB21EZ, U.K.; fax: + 44 1223 336033.

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    Cited By

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    This article is cited by 46 publications.

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2021, 143, 37, 15005–15010
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.1c07741
    Published September 8, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

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