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Ab initio quantum chemical and ReaxFF-based study of the intramolecular iminium–enamine conversion in a proline-catalyzed reaction

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Theoretical Chemistry in Belgium

Part of the book series: Highlights in Theoretical Chemistry ((HITC,volume 6))

Abstract

Among all strategies used by organic chemists to control the stereoselectivity of reactions, organocatalysis, which consists in using the chirality of a small organic molecule, is an increasingly popular method. The prolinecatalyzed aldol reaction was one of the first reported cases that demonstrated the power of organocatalysis in the field of asymmetric synthesis. Previous theoretical contributions focused on the reaction mechanism using quantum mechanics (QM) methods. We here present a theoretical study about one specific step of the proline-catalyzed aldol reaction, namely, the conversion of the iminium intermediate into the corresponding enamine. It consists of an intramolecular rearrangement that involves the transfer of a hydrogen atom. First, we investigate this transfer using modern QM models, that is, density functional theory calculations with the M06-2X functional. On the basis of these QM results, we then assess the performance of a reactive force field, ReaxFF, used in combination with molecular dynamics simulations in order to provide a complementary light on this reaction.

Published as part of the special collection of articles celebrating theoretical and computational chemistry in Belgium

Electronic supplementary material The online version of this article (doi:10.1007/s00214-012-1245-4) contains supplementary material, which is available to authorized users.

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Author information

Authors and Affiliations

  1. Laboratoire de Physico-Chimie Informatique, University of Namur, 61, rue de Bruxelles, 5000, Namur, Belgium

    Pierre O. Hubin, Laurence Leherte & Daniel P. Vercauteren

  2. CESIAM UMR CNRS 6230, Université de Nantes, 2, rue de la Houssinière, 92208, 44322, Nantes 3, France

    Denis Jacquemin

  3. Académie Royale de Belgique, University of Namur, 61, rue de Bruxelles, 5000, Namur, Belgium

    Jean-Marie André

  4. Department of Mechanical and Nuclear Engineering, Pennsylvania State University, 136 Research East Building, University Park, PA, 16802, USA

    Adri C. T. van Duin

Authors
  1. Pierre O. Hubin
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  2. Denis Jacquemin
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  3. Laurence Leherte
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  4. Jean-Marie André
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  5. Adri C. T. van Duin
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  6. Daniel P. Vercauteren
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Corresponding authors

Correspondence to Pierre O. Hubin or Daniel P. Vercauteren .

Editor information

Editors and Affiliations

  1. Laboratory of Theoretical Chemistry, University of Namur, Namur, Belgium

    Benoît Champagne

  2. Research Group of Theoretical Chemistry and Molecular Modeling, Hasselt University, Diepenbeek, Belgium

    Michael S. Deleuze

  3. Faculteit Wetenschappen, Free University of Brussels, Brussels, Belgium

    Frank De Proft

  4. Laboratory of Crystal Engineering Inst.of Condensed Matter and Nanoscience, Catholic University of Louvain, Louvain-La-Neuve, Belgium

    Tom Leyssens

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Hubin, P.O., Jacquemin, D., Leherte, L., André, JM., van Duin, A.C.T., Vercauteren, D.P. (2014). Ab initio quantum chemical and ReaxFF-based study of the intramolecular iminium–enamine conversion in a proline-catalyzed reaction. In: Champagne, B., Deleuze, M., De Proft, F., Leyssens, T. (eds) Theoretical Chemistry in Belgium. Highlights in Theoretical Chemistry, vol 6. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-41315-5_17

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