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Mechanism and Selectivity of Rhodium-Catalyzed 1:2 Coupling of Aldehydes and Allenes
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.
2013 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 135, no 20, 7647-7659 p.Article in journal (Refereed) Published
Abstract [en]

The rhodium-catalyzed highly regioselective 1:2 coupling of aldehydes and allenes was investigated by means of density functional theory calculations. Full free energy profiles were calculated, and several possible reaction pathways were evaluated. It is shown that the energetically most plausible catalytic cycle is initiated by oxidative coupling of the two allenes, which was found to be the rate-determining step of the overall reaction. Importantly, Rh allyl complexes that are able to adopt both eta(3) and eta(1) configurations were identified as key intermediates present throughout the catalytic cycle with profound implications for the selectivity of the reaction. The calculations reproduced and rationalized the experimentally observed selectivities and provided an explanation for the remarkable alteration in the product distribution when the catalyst precursor is changed from [RhCl(nbd)](2) (nbd = norbornadiene) to complexes containing noncoordinating counterions ([Rh(cod)(2)X]; X = OTf, BF4, PF6; cod = 1,5-cyclooctadiene). It turns out that the overall selectivity of the reaction is controlled by a combination of the inherent selectivities of several of the elementary steps and that both the mechanism and the nature of the selectivity-determining steps change when the catalyst is changed.

Place, publisher, year, edition, pages
2013. Vol. 135, no 20, 7647-7659 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-91838DOI: 10.1021/ja4014166ISI: 000319551000038OAI: oai:DiVA.org:su-91838DiVA: diva2:636011
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:3;

Available from: 2013-07-08 Created: 2013-07-04 Last updated: 2017-12-06Bibliographically approved

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