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Published February 24, 2016 | Published + Supplemental Material
Journal Article Open

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

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 [Cu^I(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 [Cu^I(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.

Additional Information

© 2016 The Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Received 07 Dec 2015, Accepted 16 Feb 2016, First published online 24 Feb 2016. All publication charges for this article have been paid for by the Royal Society of Chemistry. We thank Jun Myun Ahn, Dr Angel J. Di Bilio, Lawrence M. Henling, Tanvi S. Ratani, Dr David VanderVelde, Dr Jay R. Winkler, and members of the laboratory of Prof. Harry B. Gray for assistance, and we thank the Gordon and Betty Moore Foundation and the NIH (NIGMS: R01 GM109194) for funding. Photophysical studies were conducted at the Beckman Institute Laser Resource Center. M. W. J. would like to acknowledge the National Institute of Health for a Ruth L. Kirschstein National Research Service Award (F32GM116412).

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Published - c5sc04709a.pdf

Supplemental Material - c5sc04709a1_si.pdf

Supplemental Material - c5sc04709a2_si2.mol2

Supplemental Material - c5sc04709a3.cif

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August 20, 2023
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