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A theoretical study on diastereoselective oxidative dearomatization by iodoxybenzoic acid

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Abstract

The reaction mechanism of diastereoselective oxidative dearomatization by iodoxybenzoic acid of key compounds involved in the total synthesis of epicocconone analogs, which are efficient fluorophores with a wide range of applications in protein staining and separation, was studied using density functional theory. In particular, the conformational space was investigated, as was the role of the so-called hypervalent twist move, which is thought to be the rate-determining step. Both kinetic and thermodynamical aspects of the mechanism were considered from static and dynamic viewpoints, including solvent effects. The results were then rationalized using conceptual density functional theory and Bader’s atoms-in-molecules framework, which demonstrated how complementary these two approaches are when studying organic chemistry reactions theoretically.

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Acknowledgments

We gratefully acknowledge the grant ANR-BLAN-732-01 for financial support, and the Centre de Ressources Informatiques de Haute-Normandie (CRIHAN) for providing HPC resources. V.T. and L.J. thank the Centre National de la Recherche Scientifique (CNRS) for a Chaire d’Excellence at the University of Rouen.

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Authors and Affiliations

  1. Normandy Univ., COBRA UMR 6014 & FR 3038, Université de Rouen, INSA Rouen, CNRS, 1 rue Tesniére, 76821, Mont St Aignan, Cedex, France

    Vincent Tognetti, Agathe Boulangé, Philippe A. Peixoto, Xavier Franck & Laurent Joubert

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  1. Vincent Tognetti
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  2. Agathe Boulangé
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  3. Philippe A. Peixoto
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  4. Xavier Franck
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  5. Laurent Joubert
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Correspondence to Vincent Tognetti.

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This paper belongs to Topical Collection QUITEL 2013

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Tognetti, V., Boulangé, A., Peixoto, P.A. et al. A theoretical study on diastereoselective oxidative dearomatization by iodoxybenzoic acid. J Mol Model 20, 2342 (2014). https://doi.org/10.1007/s00894-014-2342-1

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