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Three-Coordinate Copper(II) Alkynyl Complex in C–C Bond Formation: The Sesquicentennial of the Glaser Coupling

Cite this: J. Am. Chem. Soc. 2020, 142, 43, 18483–18490
Publication Date (Web):September 21, 2020
https://doi.org/10.1021/jacs.0c07137
Copyright © 2020 American Chemical Society

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    Abstract

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    Copper(II) alkynyl species are proposed as key intermediates in numerous Cu-catalyzed C–C coupling reactions. Supported by a β-diketiminate ligand, the three-coordinate copper(II) alkynyl [CuII]–C≡CAr (Ar = 2,6-Cl2C6H3) forms upon reaction of the alkyne H–C≡CAr with the copper(II) tert-butoxide complex [CuII]–OtBu. In solution, this [CuII]–C≡CAr species cleanly transforms to the Glaser coupling product ArC≡C–C≡CAr and [CuI](solvent). Addition of nucleophiles R′C≡C–Li (R′ = aryl, silyl) and Ph–Li to [CuII]–C≡CAr affords the corresponding Csp–Csp and Csp–Csp2 coupled products RC≡C–C≡CAr and Ph–C≡CAr with concomitant generation of [CuI](solvent) and {[CuI]–C≡CAr}, respectively. Supported by density functional theory (DFT) calculations, redox disproportionation forms [CuIII](C≡CAr)(R) species that reductively eliminate R–C≡CAr products. [CuII]–C≡CAr also captures the trityl radical Ph3C· to give Ph3C–C≡CAr. Radical capture represents the key Csp–Csp3 bond-forming step in the copper-catalyzed C–H functionalization of benzylic substrates R–H with alkynes H–C≡CR′ (R′ = (hetero)aryl, silyl) that provide Csp–Csp3 coupled products R–C≡CR via radical relay with tBuOOtBu as oxidant.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c07137.

    • General instrumentation and physical methods, materials, synthesis and characterization data, crystallographic details and additional structures, references for synthetic and crystallographic details, computational details, and spectral data (PDF)

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