Understanding the Regioselectivity and the Molecular Mechanism of [3 + 2] Cycloaddition Reactions between Nitrous Oxide and Conjugated Nitroalkenes: A DFT Computational Study
Regiochemical aspects and the molecular mechanism of the [3 + 2] cycloaddition between nitrous oxide and conjugated nitroalkenes were evaluated on the basis of the wb97xd/6-311 + G(d) (PCM) computational study. It was found that, independently of the nature of the nitroalkene, all considered process...
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MDPI AG
2022-12-01
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Online Access: | https://www.mdpi.com/1420-3049/27/23/8441 |
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author | Ewa Dresler Aneta Wróblewska Radomir Jasiński |
author_facet | Ewa Dresler Aneta Wróblewska Radomir Jasiński |
author_sort | Ewa Dresler |
collection | DOAJ |
description | Regiochemical aspects and the molecular mechanism of the [3 + 2] cycloaddition between nitrous oxide and conjugated nitroalkenes were evaluated on the basis of the wb97xd/6-311 + G(d) (PCM) computational study. It was found that, independently of the nature of the nitroalkene, all considered processes are realized via polar, single-step mechanisms. All attempts at the localization of hypothetical zwitterionic intermediates were unsuccessful. Additionally, the DFT computational study suggested that, in the course of the reaction, the formation of respective Δ<sup>2</sup>-4-nitro-4-R<sub>1</sub>-5-R<sub>2</sub>-1-oxa-2,3-diazolines was preferred from the kinetic point of view. |
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issn | 1420-3049 |
language | English |
last_indexed | 2024-03-09T17:39:40Z |
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spelling | doaj.art-6ada973f7e4a461bbcdc799cfc1aa11f2023-11-24T11:42:15ZengMDPI AGMolecules1420-30492022-12-012723844110.3390/molecules27238441Understanding the Regioselectivity and the Molecular Mechanism of [3 + 2] Cycloaddition Reactions between Nitrous Oxide and Conjugated Nitroalkenes: A DFT Computational StudyEwa Dresler0Aneta Wróblewska1Radomir Jasiński2Łukasiewicz Research Network, Institute of Heavy Organic Synthesis “Blachownia”, Energetyków 9, 47-225 Kędzierzyn-Koźle, PolandCentre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, PolandInstitute of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, PolandRegiochemical aspects and the molecular mechanism of the [3 + 2] cycloaddition between nitrous oxide and conjugated nitroalkenes were evaluated on the basis of the wb97xd/6-311 + G(d) (PCM) computational study. It was found that, independently of the nature of the nitroalkene, all considered processes are realized via polar, single-step mechanisms. All attempts at the localization of hypothetical zwitterionic intermediates were unsuccessful. Additionally, the DFT computational study suggested that, in the course of the reaction, the formation of respective Δ<sup>2</sup>-4-nitro-4-R<sub>1</sub>-5-R<sub>2</sub>-1-oxa-2,3-diazolines was preferred from the kinetic point of view.https://www.mdpi.com/1420-3049/27/23/8441[3 + 2] cycloadditionnitrous oxidenitroalkenesmolecular mechanismmolecular electron density theoryconceptual density functional theory |
spellingShingle | Ewa Dresler Aneta Wróblewska Radomir Jasiński Understanding the Regioselectivity and the Molecular Mechanism of [3 + 2] Cycloaddition Reactions between Nitrous Oxide and Conjugated Nitroalkenes: A DFT Computational Study Molecules [3 + 2] cycloaddition nitrous oxide nitroalkenes molecular mechanism molecular electron density theory conceptual density functional theory |
title | Understanding the Regioselectivity and the Molecular Mechanism of [3 + 2] Cycloaddition Reactions between Nitrous Oxide and Conjugated Nitroalkenes: A DFT Computational Study |
title_full | Understanding the Regioselectivity and the Molecular Mechanism of [3 + 2] Cycloaddition Reactions between Nitrous Oxide and Conjugated Nitroalkenes: A DFT Computational Study |
title_fullStr | Understanding the Regioselectivity and the Molecular Mechanism of [3 + 2] Cycloaddition Reactions between Nitrous Oxide and Conjugated Nitroalkenes: A DFT Computational Study |
title_full_unstemmed | Understanding the Regioselectivity and the Molecular Mechanism of [3 + 2] Cycloaddition Reactions between Nitrous Oxide and Conjugated Nitroalkenes: A DFT Computational Study |
title_short | Understanding the Regioselectivity and the Molecular Mechanism of [3 + 2] Cycloaddition Reactions between Nitrous Oxide and Conjugated Nitroalkenes: A DFT Computational Study |
title_sort | understanding the regioselectivity and the molecular mechanism of 3 2 cycloaddition reactions between nitrous oxide and conjugated nitroalkenes a dft computational study |
topic | [3 + 2] cycloaddition nitrous oxide nitroalkenes molecular mechanism molecular electron density theory conceptual density functional theory |
url | https://www.mdpi.com/1420-3049/27/23/8441 |
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