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DFT study of the mechanism and stereoselectivity of the 1,3-dipolar cycloaddition between pyrroline-1-oxide and methyl crotonate

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Abstract

A theoretical study of the regio- and stereoselectivities of the 1,3-dipolar cycloaddition reaction between methyl crotonate and pyrroline-1-oxide has been carried out using density functional theory (DFT) at the B3LYP/6-31G(d) level of theory. The reaction has been followed by performing transition state optimization, calculations of intrinsic reaction coordinate and activation energies; the molecular mechanism of the reactions is concerted and asynchronous. The regio- and exo/endo-selectivity have been explained in terms of frontier molecular orbital interactions, local and global electrophilicity and nucleophilicity indices and an analysis of the Wiberg bond indices in the transition state. The FMO analysis and DFT-based reactivity indices showed that the regioselectivity of this reaction is controlled by the HOMOdipole–LUMOdipolarophile interaction. The activation parameters indicated favoured endo approach along the meta-pathway in agreement with the experimental results.

The molecular mechanism of the 1,3-dipolar cycloaddition reaction between pyrroline-1-oxide and methyl crotonate is theoretically investigated by DFT method at the B3LYP/6-31G* level. The transition states corresponding to the possible stereoisomeric pathways along regioisomeric reaction channels were searched, localized and optimized. The cycloaddition is favored along the reaction channel with the meta-endo adduct as major diastereomer in agreement with experiment.

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Acknowledgement

This work was supported by the Ministry of High Education of Morocco (SCH09/09) project ‘Plan d’Urgence’ and European PF7 Marie Curie PIRSES-GA-2012-317544 project CAPZEO.

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Authors and Affiliations

  1. Laboratoire de Spectroscopie, Modélisation Moléculaire, Matériaux et Environnement (LS3ME) Université Mohammed V-Agdal Faculté des Sciences, BP 1014, Rabat, Maroc

    KHADIJA MARAKCHI, OUM KALTOUM KABBAJ & NAJIA KOMIHA

  2. Laboratoire de Synthèse Organique, Organométallique et Théorique. Faculté des Sciences, Université Ibn Tofail, BP 13314, Kénitra, Maroc

    RACHIDA GHAILANE

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  1. KHADIJA MARAKCHI
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  2. RACHIDA GHAILANE
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MARAKCHI, K., GHAILANE, R., KABBAJ, O.K. et al. DFT study of the mechanism and stereoselectivity of the 1,3-dipolar cycloaddition between pyrroline-1-oxide and methyl crotonate. J Chem Sci 126, 283–292 (2014). https://doi.org/10.1007/s12039-013-0563-y

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