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Direct Synthesis of High-Valent Aryl–Cu(II) and Aryl–Cu(III) Compounds: Mechanistic Insight into Arene C–H Bond Metalation

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    Direct Synthesis of High-Valent Aryl–Cu(II) and Aryl–Cu(III) Compounds: Mechanistic Insight into Arene C–H Bond Metalation
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    † Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Tsinghua University, Beijing 100084, China
    ‡ Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
    [email protected]
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    Cite this: J. Am. Chem. Soc. 2014, 136, 17, 6326–6332
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    https://doi.org/10.1021/ja412615h
    Published April 14, 2014
    Copyright © 2014 American Chemical Society
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    Abstract

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    Copper and its salts are abundant, inexpensive, and eco-friendly and have been used as the surrogates of noble metals to effect arene C–H bond activation and transformations. Despite of the recent significant progress of the study, syntheses of high-valent arylcopper(II–III) compounds are still very rare and mechanisms of copper(II)-catalyzed reactions remain elusive. With the use of azacalix[1]arene[3]pyridines as a platform, a number of arylcopper(II) compounds were synthesized efficiently from the reaction of Cu(ClO4)2 under ambient conditions. The resulting aryl–Cu(II) compounds, which contain an unprecedented (substituted) phenyl–Cu(II) σ-bond, were stable under atmospheric conditions and can undergo facile oxidation reaction by free copper(II) ions or oxone to afford arylcopper(III) compounds in good yields. Both arylcopper(II) and arylcopper(III) compounds were characterized unambiguously by means of XRD, XPS, and NMR methods. Experimental evidence including reaction kinetics, LFER and KIE, and theoretical calculations indicated that the Cu(ClO4)2-mediated arene C–H bond activation proceeds plausibly through an electrophilic aromatic metalation pathway. The synthesis of high-valent arylcopper compounds and the reaction mechanism reported here highlight the diversity and richness of organocopper chemistry.

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    Detailed experimental procedures; characterization of all products; X-ray crystallographic files of 2b, 2g, and 3g; XPS of 2a and 3a; DPV of 2; CV and DPV of 3a; 1H and 13C NMR spectra of products; DFT calculations. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cite this: J. Am. Chem. Soc. 2014, 136, 17, 6326–6332
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