The Puzzle of the New Type of Intermediate in the Course of [2 + 2] Cycloaddition with the Participation of Conjugated Nitroalkenes: MEDT Computational Study
The phenomena of regio- and stereoselectivity and the molecular mechanism of the [2 + 2] cycloaddition reaction between (E)-2-arylnitroethenes and the ynamine molecular system were analyzed using wb97xd/6-311 + G(d) (PCM) quantumchemical calculations. It was found that, independently of the stepwise...
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2025-05-01
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| author | Radomir Jasiński Agnieszka Kącka-Zych |
| author_facet | Radomir Jasiński Agnieszka Kącka-Zych |
| author_sort | Radomir Jasiński |
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| description | The phenomena of regio- and stereoselectivity and the molecular mechanism of the [2 + 2] cycloaddition reaction between (E)-2-arylnitroethenes and the ynamine molecular system were analyzed using wb97xd/6-311 + G(d) (PCM) quantumchemical calculations. It was found that, independently of the stepwise nature of the cycloaddition, the full retention of the stereoconfiguration of the nitroalkene can be interpreted and explained. Next, the analysis of the electronic properties of the localized reaction intermediate suggests its possible zwitterionic nature. Additionally, the solvent and the substituent effect on the reaction course were also evaluated. In consequence, the proposed mechanism can be treated as general for some groups of [2 + 2] cycloaddition processes. Lastly, for the model process, the full Bonding Evolution Theory (BET) analysis along the reaction coordinate was performed. It was found that the [2 + 2] cycloaddition reaction between (E)-2-phenylonitroethene and ynamine begins with the formation of two <i>pseudoradical</i> centers at the C2 and C3 atoms. First, a C2-C3 single bond is formed in phase V by combining two <i>pseudoradical</i> centers, while the formation of a second C4-C1 single bond begins at the last, eleventh phase of the reaction path. A BET analysis of intermediate (<b>I</b>) allows it to be classified as a compound with a <i>pseudoradical</i> structure. Next to zwitterions and biradicals, it is evidently new type of intermediate on the path of the [2 + 2] cycloaddition reaction. |
| format | Article |
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| institution | DOAJ |
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| publishDate | 2025-05-01 |
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| spelling | doaj-art-6cc7d59a46ff445a81896be0a6cc646b2025-08-20T03:11:19ZengMDPI AGMolecules1420-30492025-05-013011241010.3390/molecules30112410The Puzzle of the New Type of Intermediate in the Course of [2 + 2] Cycloaddition with the Participation of Conjugated Nitroalkenes: MEDT Computational StudyRadomir Jasiński0Agnieszka Kącka-Zych1Department of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, PolandDepartment of Organic Chemistry and Technology, Cracow University of Technology, Warszawska 24, 31-155 Cracow, PolandThe phenomena of regio- and stereoselectivity and the molecular mechanism of the [2 + 2] cycloaddition reaction between (E)-2-arylnitroethenes and the ynamine molecular system were analyzed using wb97xd/6-311 + G(d) (PCM) quantumchemical calculations. It was found that, independently of the stepwise nature of the cycloaddition, the full retention of the stereoconfiguration of the nitroalkene can be interpreted and explained. Next, the analysis of the electronic properties of the localized reaction intermediate suggests its possible zwitterionic nature. Additionally, the solvent and the substituent effect on the reaction course were also evaluated. In consequence, the proposed mechanism can be treated as general for some groups of [2 + 2] cycloaddition processes. Lastly, for the model process, the full Bonding Evolution Theory (BET) analysis along the reaction coordinate was performed. It was found that the [2 + 2] cycloaddition reaction between (E)-2-phenylonitroethene and ynamine begins with the formation of two <i>pseudoradical</i> centers at the C2 and C3 atoms. First, a C2-C3 single bond is formed in phase V by combining two <i>pseudoradical</i> centers, while the formation of a second C4-C1 single bond begins at the last, eleventh phase of the reaction path. A BET analysis of intermediate (<b>I</b>) allows it to be classified as a compound with a <i>pseudoradical</i> structure. Next to zwitterions and biradicals, it is evidently new type of intermediate on the path of the [2 + 2] cycloaddition reaction.https://www.mdpi.com/1420-3049/30/11/2410[2 + 2] cycloadditionnitroalkenesstereochemistrypseudoradical intermediateDFT calculationsmechanism |
| spellingShingle | Radomir Jasiński Agnieszka Kącka-Zych The Puzzle of the New Type of Intermediate in the Course of [2 + 2] Cycloaddition with the Participation of Conjugated Nitroalkenes: MEDT Computational Study Molecules [2 + 2] cycloaddition nitroalkenes stereochemistry pseudoradical intermediate DFT calculations mechanism |
| title | The Puzzle of the New Type of Intermediate in the Course of [2 + 2] Cycloaddition with the Participation of Conjugated Nitroalkenes: MEDT Computational Study |
| title_full | The Puzzle of the New Type of Intermediate in the Course of [2 + 2] Cycloaddition with the Participation of Conjugated Nitroalkenes: MEDT Computational Study |
| title_fullStr | The Puzzle of the New Type of Intermediate in the Course of [2 + 2] Cycloaddition with the Participation of Conjugated Nitroalkenes: MEDT Computational Study |
| title_full_unstemmed | The Puzzle of the New Type of Intermediate in the Course of [2 + 2] Cycloaddition with the Participation of Conjugated Nitroalkenes: MEDT Computational Study |
| title_short | The Puzzle of the New Type of Intermediate in the Course of [2 + 2] Cycloaddition with the Participation of Conjugated Nitroalkenes: MEDT Computational Study |
| title_sort | puzzle of the new type of intermediate in the course of 2 2 cycloaddition with the participation of conjugated nitroalkenes medt computational study |
| topic | [2 + 2] cycloaddition nitroalkenes stereochemistry pseudoradical intermediate DFT calculations mechanism |
| url | https://www.mdpi.com/1420-3049/30/11/2410 |
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