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  Mechanism of the Visible-Light-Mediated Copper-Catalyzed Coupling Reaction of Phenols and Alkynes

Xiao, P., Li, C.-X., Fang, W.-H., Cui, G., & Thiel, W. (2018). Mechanism of the Visible-Light-Mediated Copper-Catalyzed Coupling Reaction of Phenols and Alkynes. Journal of the American Chemical Society, 140(44), 15099-15113. doi:10.1021/jacs.8b10387.

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 Creators:
Xiao, Pin1, Author
Li, Chun-Xiang1, Author
Fang, Wei-Hai1, Author
Cui, Ganglong1, Author
Thiel, Walter2, Author              
Affiliations:
1Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, China, ou_persistent22              
2Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              

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 Abstract: A recent experimental study reported a visible-light-mediated aerobic oxidative coupling reaction of phenol with alkynes that produces hydroxyl-functionalized aryl ketones using inexpensive CuCl as catalyst under mild conditions. Here we apply the complete active space self-consistent field (CASSCF) method and multistate second-order perturbation (MS-CASPT2) theory in combination with density functional theory (DFT) to systematically explore the entire photocatalytic reaction between phenol and phenylacetylene in acetonitrile solution in the presence of molecular oxygen and CuCl. Our main findings are as follows: (1) The visible-light-driven conversion of phenylacetylene to PhCCCu(I) occurs thermally because of efficient excited-state deactivation to the S0 state. (2) The single electron transfer from PhCCCu(I) to molecular oxygen that leads to the PhCCCu(II) cation takes place in the T1 state after an efficient S1 → T1 intersystem crossing. (3) During the initial oxidation of phenol, molecular oxygen prefers to attack the para position of the phenol radical intermediate to produce 1,4-benzoquinone, which further reacts with PhCCCu(II) to generate para-hydroxyl-substituted aryl ketones; this is the origin of the experimentally observed regioselectivity. (4) The C≡C bond of the phenylacetylene moiety is not activated by the triplet-state single electron transfer from PhCCCu(I) to molecular oxygen but is cleaved at a later stage, in the [2+2] cycloaddition between PhCCCu(II) and 1,4-benzoquinone. (5) The substrate phenol plays an active role in several hydrogen transfer and decarboxylation reactions; the barriers to these phenol-assisted reactions are lower than those for the corresponding direct or water-assisted reactions, which explains the experimental finding that adding water does not enhance the photocatalytic reaction yield. In summary, while supporting the general features of the experimentally proposed mechanism, our computational study provides detailed mechanistic insights that should be useful for understanding and further improving visible-light-induced copper-catalyzed coupling reactions.

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Language(s): eng - English
 Dates: 2018-09-262018-10-162018-11-07
 Publication Status: Published in print
 Pages: 15
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.8b10387
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Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
  Abbreviation : JACS
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 140 (44) Sequence Number: - Start / End Page: 15099 - 15113 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870