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Theoretical study of mechanism and selectivity of copper-catalyzedC−H bond amidation of indoles
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2011 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 76, no 22, 9246-9252 p.Article in journal (Refereed) Published
Abstract [en]

Density functional theory calculations are used to study the reaction mechanism and origins of C2 selectivity in a copper(I)-catalyzed amidation of indoles. It is shown that concerted metalation−deprotonation is not able to reproduce the observed regioselectivity. Instead, an unprecedented mechanism based on a four-center reductive elimination is proposed to be responsible for the reaction outcome. This mechanism has a lower reaction barrier and is able to reproduce the experimentally observed selectivity. A possible alternative mechanism involving a Cu(II) species instead of Cu(III) is presented, but it is shown that higher energy barriers are associated with this mechanism. An important technical detail is that addition of dispersion effects to the B3LYP results is necessary to reproduce the observed selectivity, although not important for the overall mechanistic proposal.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2011. Vol. 76, no 22, 9246-9252 p.
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-69513DOI: 10.1021/jo201447eISI: 000296754400006OAI: oai:DiVA.org:su-69513DiVA: diva2:477094
Funder
Swedish Research Council
Note
authorCount :3Available from: 2012-01-12 Created: 2012-01-12 Last updated: 2017-12-08Bibliographically approved

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