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Cobalt-Catalyzed C(sp2)–CN Bond Activation: Cross-Electrophile Coupling for Biaryl Formation and Mechanistic Insight

  • Céline Dorval
    Céline Dorval
    Laboratoire de Chimie Moléculaire, CNRS UMR 9168, École Polytechnique, Institut Polytechnique de Paris, Route de Saclay, 91128 Palaiseau Cedex, France
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  • , 
  • Maxime Tricoire
    Maxime Tricoire
    Laboratoire de Chimie Moléculaire, CNRS UMR 9168, École Polytechnique, Institut Polytechnique de Paris, Route de Saclay, 91128 Palaiseau Cedex, France
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  • , 
  • Jeanne-Marie Begouin
    Jeanne-Marie Begouin
    Laboratoire de Chimie Moléculaire, CNRS UMR 9168, École Polytechnique, Institut Polytechnique de Paris, Route de Saclay, 91128 Palaiseau Cedex, France
    More by Jeanne-Marie Begouin
  • , 
  • Vincent Gandon*
    Vincent Gandon
    Laboratoire de Chimie Moléculaire, CNRS UMR 9168, École Polytechnique, Institut Polytechnique de Paris, Route de Saclay, 91128 Palaiseau Cedex, France
    Institut de Chimie Moléculaire et des Matériaux d’Orsay (ICMMO), CNRS UMR 8182, Université Paris-Saclay, Bâtiment 420, 91405 Orsay Cedex, France
    *Email: [email protected]
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  • , and 
  • Corinne Gosmini*
    Corinne Gosmini
    Laboratoire de Chimie Moléculaire, CNRS UMR 9168, École Polytechnique, Institut Polytechnique de Paris, Route de Saclay, 91128 Palaiseau Cedex, France
    *Email: [email protected]
    More by Corinne Gosmini
    Orcidhttp://orcid.org/0000-0002-1355-2301
Cite this: ACS Catal. 2020, 10, 21, 12819–12827
Publication Date (Web):October 19, 2020
https://doi.org/10.1021/acscatal.0c03903
Copyright © 2020 American Chemical Society
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    Abstract

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    Herein, we report a cross-electrophile coupling of benzonitrile derivatives and aryl halides with a simple cobalt-based catalytic system under mild conditions to form biaryl compounds. Even though the cobalt catalyst is able to activate the C(sp2)–CN bond alone, the use of the AlMe3 Lewis acid enhances the reactivity of benzonitriles and improves the cross-selectivity with barely any influence on the functional group compatibility. X-ray structure determination of an original low-valent cobalt species combined with catalytic and stoichiometric reactions reveals a catalytically active cobalt(I) species toward the aryl halide partner. On the other hand, experimental insights, including cyclic voltammetry experiments, suggest the involvement of a cobalt complex of a lower oxidation state to activate the benzonitrile derivative. Finally, density functional theory calculations support the proposed mechanistic cycle involving two low-valent cobalt species of different oxidation states to perform the reaction.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.0c03903.

    • Reaction optimization tables, mechanistic and stoichiometric studies, synthetic procedures, cyclic voltammetry, DFT calculations, and characterization data of NMR spectra and X-ray data for Co-Red (PDF)

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