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Issue 7, 2016
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A mechanistic investigation of the photoinduced, copper-mediated cross-coupling of an aryl thiol with an aryl halide

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Abstract

Photoinduced, copper-catalyzed cross-coupling can offer a complementary approach to thermal (non-photoinduced) methods for generating C–X (X = C, N, O, S, etc.) bonds. In this report, we describe the first detailed mechanistic investigation of one of the processes that we have developed, specifically, the (stoichiometric) coupling of a copper–thiolate with an aryl iodide. In particular, we focus on the chemistry of a discrete [CuI(SAr)2] complex (Ar = 2,6-dimethylphenyl), applying a range of techniques, including ESI-MS, cyclic voltammetry, transient luminescence spectroscopy, optical spectroscopy, DFT calculations, Stern–Volmer analysis, EPR spectroscopy, actinometry, and reactivity studies. The available data are consistent with the viability of a pathway in which photoexcited [CuI(SAr)2]* serves as an electron donor to an aryl iodide to afford an aryl radical, which then reacts in cage with the newly generated copper(II)–thiolate to furnish the cross-coupling product in a non-chain process.

Graphical abstract: A mechanistic investigation of the photoinduced, copper-mediated cross-coupling of an aryl thiol with an aryl halide

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Publication details

The article was received on 07 Dec 2015, accepted on 16 Feb 2016 and first published on 24 Feb 2016


Article type: Edge Article
DOI: 10.1039/C5SC04709A
Citation: Chem. Sci., 2016,7, 4091-4100
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    A mechanistic investigation of the photoinduced, copper-mediated cross-coupling of an aryl thiol with an aryl halide

    M. W. Johnson, K. I. Hannoun, Y. Tan, G. C. Fu and J. C. Peters, Chem. Sci., 2016, 7, 4091
    DOI: 10.1039/C5SC04709A

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