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Kinetics and mechanism of the 1,3-dipolar cycloaddition of nitrilimine with thione-containing dipolarophile: a detailed DFT study

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Abstract

The 1,3-dipolar cycloadditions are extensively used for the preparation of five-membered heterocycles. A mechanism consisting of two pathways was proposed for production of two regioisomers of the 1,3-dipolar cycloaddition of the nitrilimine and a thione-containing dipolarophile. Here, we have investigated the kinetics and mechanism of this reaction using density functional theory. Two possible mechanisms of A and B have been investigated in which Cl− is present in the structure of the nitrilimine reactant in the case of mechanism A, while it is absent in the case of mechanism B. Mechanism A, involving Cl−, has higher barrier energy than mechanism B, and so is rejected. Mechanism B involves two pathways, I and II, which lead to two regioisomers with different percentages in the products. Both of the pathways are one-step. Pathway II involves the attack of the nitrogen atom of the nitrilimine on the carbon atom of the C=S group of the dipolarophile. The product of pathway II is kinetically and thermodynamically a more favorable product than its regioisomer produced in the other pathway. The obtained results are in agreement with the experimental results.

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Authors and Affiliations

  1. Department of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, Iran

    Atiye Bazian, S. Ali Beyramabadi, Abolghasem Davoodnia, Mehdi Pordel & Mohammad Reza Bozorgmehr

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  1. Atiye Bazian
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  2. S. Ali Beyramabadi
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  3. Abolghasem Davoodnia
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  4. Mehdi Pordel
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  5. Mohammad Reza Bozorgmehr
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Correspondence to S. Ali Beyramabadi.

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Bazian, A., Beyramabadi, S.A., Davoodnia, A. et al. Kinetics and mechanism of the 1,3-dipolar cycloaddition of nitrilimine with thione-containing dipolarophile: a detailed DFT study. Res Chem Intermed 42, 6125–6141 (2016). https://doi.org/10.1007/s11164-016-2449-3

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  • DOI: https://doi.org/10.1007/s11164-016-2449-3

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