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Mechanistic study of bismuth-catalyzed direct benzylation of 2,4-pentanediones: the case of BiCl3 and generalization

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Abstract

At present, we investigate the mechanisms for bismuth-catalyzed direct benzylation of 2,4-pentanediones using various density functional theories and post-Hartree–Fock ab initio methods. First, we deeply consider the role of BiCl3, where six scenarios are proposed. All of them start with the formation of a weakly bound complex between the BiCl3 catalyst and the alcohol or the dione. The most favorable one corresponds to the direct access to the products via a unique transition state (SN2-type mechanism). We also examined the effects of various nonpolar and polar solvents, which are viewed to slightly affect the energy profiles for SN2 and internal nucleophilic substitution (SNi) types of mechanism, whereas strong perturbations are observed for SN1 mechanism. For instance, the later one becomes the most thermodynamically favorable in DMSO solvent. In addition, several classes of benzyl alcohols and catalysts (BiX3, where X = Cl, Br, I, NO3, and OTf) were considered within the framework of SN2 and SNi mechanisms. The reactivity of these alcohols increases going from primary to secondary to tertiary. These findings are in line with the present available experimental results. Finally, our computations suggest that Bi(NO3)3 could be an excellent catalyst for the title reaction.

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Acknowledgments

This research was financially supported by the Tunisian Ministry of Higher Education and Research and by a Marie Curie International Research Staff Exchange Scheme Fellowship within the 7th European Community Framework Program under Grant No PIRSES-GA-2012-31754, the COST Action CM1405 MOLIM.

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Authors and Affiliations

  1. Unité de Recherche Physico-Chimie des Matériaux à l’Etat Condensé, Département de Chimie, Faculté des Sciences de Tunis, Université Tunis El Manar, 2092, Tunis, Tunisia

    K. Harrath & S. Boughdiri

  2. Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, Université Paris-Est, 5 bd Descartes, 77454, Marne-la-Vallée, France

    R. Linguerri & M. Hochlaf

Authors
  1. K. Harrath
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  2. S. Boughdiri
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  3. R. Linguerri
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  4. M. Hochlaf
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Correspondence to S. Boughdiri, R. Linguerri or M. Hochlaf.

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Harrath, K., Boughdiri, S., Linguerri, R. et al. Mechanistic study of bismuth-catalyzed direct benzylation of 2,4-pentanediones: the case of BiCl3 and generalization. Theor Chem Acc 135, 2 (2016). https://doi.org/10.1007/s00214-015-1758-8

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