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...
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2022-12-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/27/23/8441 |
| _version_ | 1797462585649397760 |
|---|---|
| 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. |
| first_indexed | 2024-03-09T17:39:40Z |
| format | Article |
| id | doaj.art-6ada973f7e4a461bbcdc799cfc1aa11f |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T17:39:40Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| 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 |
| work_keys_str_mv | AT ewadresler understandingtheregioselectivityandthemolecularmechanismof32cycloadditionreactionsbetweennitrousoxideandconjugatednitroalkenesadftcomputationalstudy AT anetawroblewska understandingtheregioselectivityandthemolecularmechanismof32cycloadditionreactionsbetweennitrousoxideandconjugatednitroalkenesadftcomputationalstudy AT radomirjasinski understandingtheregioselectivityandthemolecularmechanismof32cycloadditionreactionsbetweennitrousoxideandconjugatednitroalkenesadftcomputationalstudy |