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Caution in the Use of Nonlinear Effects as a Mechanistic Tool for Catalytic Enantioconvergent Reactions: Intrinsic Negative Nonlinear Effects in the Absence of Higher-Order Species
Stockholm University, Faculty of Science, Department of Organic Chemistry. California Institute of Technology, United States; University of Warsaw, Poland.
Number of Authors: 2
2017 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 139, no 11, 4225-4229 p.Article in journal (Refereed) Published
Abstract [en]

Investigation of the dependence of product enantiometric excess (ee) on catalyst ee is a widely used tool to probe the mechanism of an enantioselective reaction; in particular, the observation of a nonlinear relationship is usually interpreted as an indication of the presence of one or more species that contain at least two units of the chiral entity. In this report, we demonstrate that catalytic enantioconvergent reactions can display an intrinsic negative nonlinear effect that originates purely from the kinetic characteristics of certain enantioconvergent processes and is independent of possible aggregation of the chiral entity. Specifically, this intrinsic negative nonlinear effect can arise when there is a kinetic resolution of the racemic starting material, and its magnitude is correlated with the selectivity factor and the conversion; the dependence on conversion provides a ready means to distinguish it from a more conventional nonlinear effect. We support our analysis with experimental data for two distinct enantioconvergent processes, catalyzed by a chiral phosphine and the other by a chiral Pd/phosphine complex.

Place, publisher, year, edition, pages
2017. Vol. 139, no 11, 4225-4229 p.
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-142647DOI: 10.1021/jacs.7b01826ISI: 000397477700043PubMedID: 28276679OAI: oai:DiVA.org:su-142647DiVA: diva2:1095517
Available from: 2017-05-15 Created: 2017-05-15 Last updated: 2017-05-15Bibliographically approved

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