A DFT Study on the Molecular Mechanism of Additions of Electrophilic and Nucleophilic Carbenes to Non-Enolizable Cycloaliphatic Thioketones
The molecular mechanisms of addition of dihalocarbenes and dimethoxycarbene to thioketones derived from 2,2,4,4-tetrmethylcyclobutane-1,3-dione were examined on the basis of the DFT wb97xd/6-311g(d,p)(PCM) calculations. Obtained results demonstrated that the examined processes exhibit polar nature a...
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MDPI AG
2021-09-01
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| Online Access: | https://www.mdpi.com/1420-3049/26/18/5562 |
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| author | Grzegorz Mlostoń Karolina Kula Radomir Jasiński |
| author_facet | Grzegorz Mlostoń Karolina Kula Radomir Jasiński |
| author_sort | Grzegorz Mlostoń |
| collection | DOAJ |
| description | The molecular mechanisms of addition of dihalocarbenes and dimethoxycarbene to thioketones derived from 2,2,4,4-tetrmethylcyclobutane-1,3-dione were examined on the basis of the DFT wb97xd/6-311g(d,p)(PCM) calculations. Obtained results demonstrated that the examined processes exhibit polar nature and in the case of electrophilic dichloro-, and dibromocarbenes are initiated by the attack of carbene species onto the sulfur atom of the C=S group. Remarkably, reactions involving more electrophilic carbenes (dichloro-, and dibromocarbene) proceeds via stepwise mechanism involving thiocarbonyl ylide as a transient intermediate. In contrast, analogous reactions with nucleophilic dimethoxycarbene occur via a single step reaction, which can be considered as the [2 + 1] cycloaddition reaction initiated by the attack onto the C=S bond. A computational study showed that difluorocarbene tends to react as a nucleophilic species and resembles rather dimethoxycarbene and not typical dihalocarbene species. Significantly higher reactivity of the thioketone unit in comparison to the ketone group, both present in 3-thioxo-2,2,4,4-tetramthylcyclobutanone molecule, was rationalized in the light of DFT computational study. |
| first_indexed | 2024-03-10T07:24:40Z |
| format | Article |
| id | doaj.art-f221771ba5604028ac67849745f46e38 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T07:24:40Z |
| publishDate | 2021-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-f221771ba5604028ac67849745f46e382023-11-22T14:24:59ZengMDPI AGMolecules1420-30492021-09-012618556210.3390/molecules26185562A DFT Study on the Molecular Mechanism of Additions of Electrophilic and Nucleophilic Carbenes to Non-Enolizable Cycloaliphatic ThioketonesGrzegorz Mlostoń0Karolina Kula1Radomir Jasiński2Department of Organic and Applied Chemistry, University of Łódź, Tamka 12, PL-91-403 Łódź, PolandInstitute of Organic Chemistry & Technology, Cracow University of Technology, Warszawska 24, PL-31-155 Krakow, PolandInstitute of Organic Chemistry & Technology, Cracow University of Technology, Warszawska 24, PL-31-155 Krakow, PolandThe molecular mechanisms of addition of dihalocarbenes and dimethoxycarbene to thioketones derived from 2,2,4,4-tetrmethylcyclobutane-1,3-dione were examined on the basis of the DFT wb97xd/6-311g(d,p)(PCM) calculations. Obtained results demonstrated that the examined processes exhibit polar nature and in the case of electrophilic dichloro-, and dibromocarbenes are initiated by the attack of carbene species onto the sulfur atom of the C=S group. Remarkably, reactions involving more electrophilic carbenes (dichloro-, and dibromocarbene) proceeds via stepwise mechanism involving thiocarbonyl ylide as a transient intermediate. In contrast, analogous reactions with nucleophilic dimethoxycarbene occur via a single step reaction, which can be considered as the [2 + 1] cycloaddition reaction initiated by the attack onto the C=S bond. A computational study showed that difluorocarbene tends to react as a nucleophilic species and resembles rather dimethoxycarbene and not typical dihalocarbene species. Significantly higher reactivity of the thioketone unit in comparison to the ketone group, both present in 3-thioxo-2,2,4,4-tetramthylcyclobutanone molecule, was rationalized in the light of DFT computational study.https://www.mdpi.com/1420-3049/26/18/5562carbenesthioketonesorganic reactions mechanismsDFT calculationsmolecular electron density theory |
| spellingShingle | Grzegorz Mlostoń Karolina Kula Radomir Jasiński A DFT Study on the Molecular Mechanism of Additions of Electrophilic and Nucleophilic Carbenes to Non-Enolizable Cycloaliphatic Thioketones Molecules carbenes thioketones organic reactions mechanisms DFT calculations molecular electron density theory |
| title | A DFT Study on the Molecular Mechanism of Additions of Electrophilic and Nucleophilic Carbenes to Non-Enolizable Cycloaliphatic Thioketones |
| title_full | A DFT Study on the Molecular Mechanism of Additions of Electrophilic and Nucleophilic Carbenes to Non-Enolizable Cycloaliphatic Thioketones |
| title_fullStr | A DFT Study on the Molecular Mechanism of Additions of Electrophilic and Nucleophilic Carbenes to Non-Enolizable Cycloaliphatic Thioketones |
| title_full_unstemmed | A DFT Study on the Molecular Mechanism of Additions of Electrophilic and Nucleophilic Carbenes to Non-Enolizable Cycloaliphatic Thioketones |
| title_short | A DFT Study on the Molecular Mechanism of Additions of Electrophilic and Nucleophilic Carbenes to Non-Enolizable Cycloaliphatic Thioketones |
| title_sort | dft study on the molecular mechanism of additions of electrophilic and nucleophilic carbenes to non enolizable cycloaliphatic thioketones |
| topic | carbenes thioketones organic reactions mechanisms DFT calculations molecular electron density theory |
| url | https://www.mdpi.com/1420-3049/26/18/5562 |
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