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Mechanistic Insights into the Catalytic Asymmetric Allylboration of Ketones: Brønsted or Lewis Acid Activation?

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Unilever Centre for Molecular Science Informatics, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, U.K., and Instituto de Química Rosario (CONICET), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, Rosario (2000), Argentina
†University of Cambridge.
‡Universidad Nacional de Rosario.
Cite this: Org. Lett. 2009, 11, 1, 37–40
Publication Date (Web):November 26, 2008
https://doi.org/10.1021/ol802270u
Copyright © 2008 American Chemical Society

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    Abstract

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    Binaphthol ligands promote the enantioselective addition of allylboronates to ketones. In this study, we use DFT calculations to establish the identity of the reacting chiral species. Our results show that a cyclic Lewis acid-activated boronate is the most reactive species on the basis of calculated energy barriers, and it is only this species that leads to the correct enantiomer. The stereoinduction can be rationalized in terms of the competing chairlike transition structures.

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    Cartesian coordinates and energies of all the stationary points reported in the paper; values of imaginary frequencies of all TSs; optimized geometries not included in the paper; energies of the FMOs of the reactants. This material is available free of charge via the Internet at http://pubs.acs.org.

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