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Characterization and Reactivity of Copper(II) and Copper(III) σ-Aryl Intermediates in Aminoquinoline-Directed C–H Functionalization

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    Characterization and Reactivity of Copper(II) and Copper(III) σ-Aryl Intermediates in Aminoquinoline-Directed C–H Functionalization
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2023, 145, 33, 18253–18259
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    https://doi.org/10.1021/jacs.3c00914
    Published August 8, 2023
    Copyright © 2023 American Chemical Society
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    Abstract

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    Over the past decade, numerous reports have focused on the development and applications of Cu-mediated C–H functionalization reactions; however, to date, little is known about the Cu intermediates involved in these transformations. This paper details the observation and characterization of CuII and CuIII intermediates in aminoquinoline-directed C(sp2)–H functionalization of a fluoroarene substrate. An initial C(sp2)–H activation at CuII occurs at room temperature to afford an isolable anionic cyclometalated CuII complex. This complex undergoes single-electron oxidation with ferrocenium or AgI salts under mild conditions (5 min at room temperature) to afford C(sp2)–C(sp2) or C(sp2)–NO2 coupling products. Spectroscopic studies implicate the formation of a transient diamagnetic CuIII-σ-aryl intermediate that undergoes either (i) a second C(sp2)–H activation at CuIII followed by C–C bond-forming reductive elimination or (ii) reaction with a NO2– nucleophile and C(sp2)–NO2 coupling.

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    CCDC 2235935 and 2235936 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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    This article is cited by 15 publications.

    1. Jia-Yi Ma, Qi-Jun Yao, Lu-Chen Jiang, Fan-Rui Huang, Qiang Yue, Bing-Feng Shi. Copper-Mediated Enantioselective C–H Thiolation of Ferrocenes Enabled by the BINOL Ligand. Journal of the American Chemical Society 2025, 147 (8) , 7061-7069. https://doi.org/10.1021/jacs.4c18255
    2. Lukass Lukasevics, George N. Oh, Xiqu Wang, Liene Grigorjeva, Olafs Daugulis. Mechanistic Investigations of Cobalt-Catalyzed, Aminoquinoline-Directed C(sp2)–H Bond Functionalization. Journal of the American Chemical Society 2025, 147 (3) , 2476-2490. https://doi.org/10.1021/jacs.4c13086
    3. Su Chen, Decai Ding, Lingfeng Yin, Xiao Wang, Jeanette A. Krause, Wei Liu. Overcoming Copper Reduction Limitation in Asymmetric Substitution: Aryl-Radical-Enabled Enantioconvergent Cyanation of Alkyl Iodides. Journal of the American Chemical Society 2024, 146 (46) , 31982-31991. https://doi.org/10.1021/jacs.4c11888
    4. Emily L. Nolan, Fengrui Qu, Melanie S. Sanford. Exploration of Organometallic Cobalt Intermediates in an Aminoquinoline-Directed Dehydrogenative Dimerization Reaction. Organometallics 2024, 43 (19) , 2165-2168. https://doi.org/10.1021/acs.organomet.4c00313
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    6. Wenhao Yan, Andrew T. Poore, Lingfeng Yin, Samantha Carter, Yeu-Shiuan Ho, Chao Wang, Stephen C. Yachuw, Yu-Ho Cheng, Jeanette A. Krause, Mu-Jeng Cheng, Shiyu Zhang, Shiliang Tian, Wei Liu. Catalytically Relevant Organocopper(III) Complexes Formed through Aryl-Radical-Enabled Oxidative Addition. Journal of the American Chemical Society 2024, 146 (22) , 15176-15185. https://doi.org/10.1021/jacs.4c01668
    7. Bofei Wang, Avijit Hazra, Gojko Lalic. Regio- and Diastereoselective Synthesis of E-Allylic Amines through Hydroalkylation of Terminal Alkynes. ACS Catalysis 2024, 14 (8) , 6021-6027. https://doi.org/10.1021/acscatal.4c00853
    8. Maxwell S. Reese, Mitchell G. Bonanno, Jamey K. Bower, Curtis E. Moore, Shiyu Zhang. C–N Bond Formation at Discrete CuIII–Aryl Complexes. Journal of the American Chemical Society 2023, 145 (49) , 26810-26816. https://doi.org/10.1021/jacs.3c09260
    9. Wenhao Yan, Samantha Carter, Chi-Tien Hsieh, Jeanette A. Krause, Mu-Jeng Cheng, Shiyu Zhang, Wei Liu. Copper–Carbon Homolysis Competes with Reductive Elimination in Well-Defined Copper(III) Complexes. Journal of the American Chemical Society 2023, 145 (48) , 26152-26159. https://doi.org/10.1021/jacs.3c08510
    10. Andrés García-Viada, Juan C. Carretero, Javier Adrio, Nuria Rodríguez. Insights into the mechanism of 3d transition-metal-catalyzed directed C(sp 3 )–H bond functionalization reactions. Chemical Society Reviews 2025, 54 (9) , 4353-4390. https://doi.org/10.1039/D4CS00657G
    11. Alejandra Pita-Milleiro, Nereida Hidalgo, Juan J. Moreno, Israel Fernández, Jesús Campos. An open-shell Ir(II)/Ir(IV) redox couple outperforms an Ir(I)/Ir(III) pair in olefin isomerization. Nature Chemistry 2025, 17 (4) , 606-613. https://doi.org/10.1038/s41557-024-01722-7
    12. Yuhang Su, Zhi‐Jiang Jiang, Jiawei Han, Lujie Duan, Jian‐Fei Bai, Jia Chen, Zhanghua Gao. Copper(II)‐Catalyzed Regioselective H/D Exchange Based on Reversible C−H Activation. Chemistry – A European Journal 2024, 30 (72) https://doi.org/10.1002/chem.202403121
    13. Daniel Pla, Montserrat Ferrer, Montserrat Gómez, Manuel Martinez Lopez. Kinetico‐Mechanistic Studies of Cu(II)‐Mediated Cyclization of Imines via C−H Bond Activations. European Journal of Inorganic Chemistry 2024, 27 (36) https://doi.org/10.1002/ejic.202400564
    14. Jinling Li, Junjie Zhao, Teck-Peng Loh. Photoredox-Catalyzed C(sp2)–H Bond Functionalization Reactions: A Short Account. Synlett 2024, 35 (08) , 840-850. https://doi.org/10.1055/a-2193-2682
    15. Lingfeng Yin, Wei Liu. Stable oganocopper(III) complexes generated via oxidative addition. Science Bulletin 2024, 69 (3) , 288-289. https://doi.org/10.1016/j.scib.2023.12.020
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2023, 145, 33, 18253–18259
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.3c00914
    Published August 8, 2023
    Copyright © 2023 American Chemical Society
    Request reuse permissions

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