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A mechanistic MEDT study of the competitive catalysed [4+2] and [2+2] cycloaddition reactions between 1-methyl-1-phenylallene and methyl acrylate: the role of Lewis acid on the mechanism and selectivity

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Abstract

The selectivity and the nature of the mechanism of the competitive Lewis acid catalysed [4+2]/[2+2] cycloaddition reactions of 1-methyl-1-phenylallene (MPA) with methylacrylate (MA) have been theoretically studied within the Molecular Electron Density Theory using DFT methods at the B3LYP/6-31G(d) theoretical level. DFT reactivity indices indicate that MPA is a strong nucleophile and the LA-MA complex is a strong electrophile. The coordination of LA to MA enhances the reaction rate and increases the asynchronicity of the [4+2] CA reaction, changes the nature of the mechanism from one step to stepwise for the [2+2] CA reaction and increases the polar character of these cycloaddition reactions, which become demands a relatively low activation energy. Analysis of different energy profiles indicates that these competitive LA-catalysed CA reactions favour the formation of a mixture of meta regioisomers in both types of cycloaddition, in which the [4+2] cycloadducts were obtained in majority amount, in agreement with the experiment. Analysis based on Electron Localisation Function topological shows that the favoured [4+2] CA reaction takes place through a non-concerted two-stage one-step mechanism.

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Authors and Affiliations

  1. Laboratoire de Synthèse et Biocatalyse Organique, Département de Chimie, Faculté des Sciences, Université Badji Mokhtar Annaba, BP 12, 23000, Annaba, Algeria

    Leila Barama, Brahim Bayoud, Fouad Chafaa, Abdelmalek Khorief Nacereddine & Abdelhafid Djerourou

  2. Département de Chimie, Faculté des Sciences, Université Saad Dahleb Blida 1, Route de Soumâa, BP 270, 09000, Blida, Algeria

    Fouad Chafaa

  3. Département de Physique et Chimie, Ecole Normale Supérieure d’Enseignement Technologique de Skikda, Cité des frères Boucetta, Azzaba, Skikda, Algeria

    Abdelmalek Khorief Nacereddine

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  1. Leila Barama
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  2. Brahim Bayoud
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  3. Fouad Chafaa
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  4. Abdelmalek Khorief Nacereddine
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  5. Abdelhafid Djerourou
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Correspondence to Abdelmalek Khorief Nacereddine.

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Barama, L., Bayoud, B., Chafaa, F. et al. A mechanistic MEDT study of the competitive catalysed [4+2] and [2+2] cycloaddition reactions between 1-methyl-1-phenylallene and methyl acrylate: the role of Lewis acid on the mechanism and selectivity. Struct Chem 29, 1709–1721 (2018). https://doi.org/10.1007/s11224-018-1152-y

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  • DOI: https://doi.org/10.1007/s11224-018-1152-y

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