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The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study
The regioselective zw-type [3 + 2] cycloaddition (32CA) reactions of a series of aryl-substituted nitrile N-oxides (NOs) with trichloronitropropene (TNP) have been both experimentally and theoretically studied within the Molecular Electron Density Theory (MEDT). Zwitterionic NOs behave as moderate n...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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MDPI
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8622200/ https://www.ncbi.nlm.nih.gov/pubmed/34833866 http://dx.doi.org/10.3390/molecules26226774 |
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author | Zawadzińska, Karolina Ríos-Gutiérrez, Mar Kula, Karolina Woliński, Przemysław Mirosław, Barbara Krawczyk, Tomasz Jasiński, Radomir |
author_facet | Zawadzińska, Karolina Ríos-Gutiérrez, Mar Kula, Karolina Woliński, Przemysław Mirosław, Barbara Krawczyk, Tomasz Jasiński, Radomir |
author_sort | Zawadzińska, Karolina |
collection | PubMed |
description | The regioselective zw-type [3 + 2] cycloaddition (32CA) reactions of a series of aryl-substituted nitrile N-oxides (NOs) with trichloronitropropene (TNP) have been both experimentally and theoretically studied within the Molecular Electron Density Theory (MEDT). Zwitterionic NOs behave as moderate nucleophiles while TNP acts as a very strong electrophile in these polar 32CA reactions of forward electron density flux, which present moderate activation Gibbs free energies of 22.8–25.6 kcal·mol(−1) and an exergonic character of 28.4 kcal·mol(−1) that makes them irreversible and kinetically controlled. The most favorable reaction is that involving the most nucleophilic MeO-substituted NO. Despite Parr functions correctly predicting the experimental regioselectivity with the most favorable O-CCCl(3) interaction, these reactions follow a two-stage one-step mechanism in which formation of the O-C(CCl(3)) bond takes place once the C-C(NO(2)) bond is already formed. The present MEDT concludes that the reactivity differences in the series of NOs come from their different nucleophilic activation and polar character of the reactions, rather than any mechanistic feature. |
format | Online Article Text |
id | pubmed-8622200 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-86222002021-11-27 The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study Zawadzińska, Karolina Ríos-Gutiérrez, Mar Kula, Karolina Woliński, Przemysław Mirosław, Barbara Krawczyk, Tomasz Jasiński, Radomir Molecules Article The regioselective zw-type [3 + 2] cycloaddition (32CA) reactions of a series of aryl-substituted nitrile N-oxides (NOs) with trichloronitropropene (TNP) have been both experimentally and theoretically studied within the Molecular Electron Density Theory (MEDT). Zwitterionic NOs behave as moderate nucleophiles while TNP acts as a very strong electrophile in these polar 32CA reactions of forward electron density flux, which present moderate activation Gibbs free energies of 22.8–25.6 kcal·mol(−1) and an exergonic character of 28.4 kcal·mol(−1) that makes them irreversible and kinetically controlled. The most favorable reaction is that involving the most nucleophilic MeO-substituted NO. Despite Parr functions correctly predicting the experimental regioselectivity with the most favorable O-CCCl(3) interaction, these reactions follow a two-stage one-step mechanism in which formation of the O-C(CCl(3)) bond takes place once the C-C(NO(2)) bond is already formed. The present MEDT concludes that the reactivity differences in the series of NOs come from their different nucleophilic activation and polar character of the reactions, rather than any mechanistic feature. MDPI 2021-11-09 /pmc/articles/PMC8622200/ /pubmed/34833866 http://dx.doi.org/10.3390/molecules26226774 Text en © 2021 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Zawadzińska, Karolina Ríos-Gutiérrez, Mar Kula, Karolina Woliński, Przemysław Mirosław, Barbara Krawczyk, Tomasz Jasiński, Radomir The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study |
title | The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study |
title_full | The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study |
title_fullStr | The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study |
title_full_unstemmed | The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study |
title_short | The Participation of 3,3,3-Trichloro-1-nitroprop-1-ene in the [3 + 2] Cycloaddition Reaction with Selected Nitrile N-Oxides in the Light of the Experimental and MEDT Quantum Chemical Study |
title_sort | participation of 3,3,3-trichloro-1-nitroprop-1-ene in the [3 + 2] cycloaddition reaction with selected nitrile n-oxides in the light of the experimental and medt quantum chemical study |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8622200/ https://www.ncbi.nlm.nih.gov/pubmed/34833866 http://dx.doi.org/10.3390/molecules26226774 |
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