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

Johnson, Miles W. and Hannoun, Kareem I. and Tan, Yichen and Fu, Gregory C. and Peters, Jonas C. (2016) A mechanistic investigation of the photoinduced, copper-mediated cross-coupling of an aryl thiol with an aryl halide. Chemical Science, 7 . pp. 4091-4100. ISSN 2041-6520. PMCID PMC5201211. https://resolver.caltech.edu/CaltechAUTHORS:20160323-130838018

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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 [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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1039/c5sc04709aDOIArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5201211/PubMed CentralArticle
ORCID:
AuthorORCID
Fu, Gregory C.0000-0002-0927-680X
Peters, Jonas C.0000-0002-6610-4414
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. 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).
Funders:
Funding AgencyGrant Number
Gordon and Betty Moore FoundationUNSPECIFIED
NIHR01 GM109194
NIH Predoctoral FellowshipF32GM116412
PubMed Central ID:PMC5201211
Record Number:CaltechAUTHORS:20160323-130838018
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160323-130838018
Official Citation:A mechanistic investigation of the photoinduced, copper-mediated cross-coupling of an aryl thiol with an aryl halide Miles W. Johnson, Kareem I. Hannoun, Yichen Tan, Gregory C. Fu and Jonas C. Peters Chem. Sci., 2016, 7, 4091-4100 DOI: 10.1039/C5SC04709A
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:65627
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:25 Mar 2016 14:55
Last Modified:27 Feb 2020 21:44

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