A DFT study on the molecular mechanism of additions of electrophilic and nucleophilic carbenes to non-enolizable cycloaliphatic thioketones
Authors:
- Grzegorz Mlostoń,
- Karolina Kula,
- Radomir Jasiński
Abstract
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.
- Record ID
- CUT0c7d4f44abbe4a919138bf5acc3e13e1
- Publication categories
- ;
- Author
- Journal series
- Molecules, ISSN , e-ISSN 1420-3049, Biweekly
- Issue year
- 2021
- Vol
- 26
- No
- 18
- Pages
- [1-14]
- Article number
- 5562
- Other elements of collation
- schem.; tab.; wykr.; Bibliografia (na s.) - 12-14; Bibliografia (liczba pozycji) - 59; Oznaczenie streszczenia - Abstr.; Numeracja w czasopiśmie - Vol. 26, Iss. 18, Spec. Iss.
- Substantive notes
- Special Issue: Advances in Organic Synthesis: A Theme Issue in Honor of Professor Mieczysław Mąkosza
- Keywords in English
- carbenes, thioketones, organic reactions mechanisms, DFT calculations, molecular electron density theory
- DOI
- DOI:10.3390/molecules26185562 Opening in a new tab
- URL
- https://www.mdpi.com/1420-3049/26/18/5562 Opening in a new tab
- Language
- eng (en) English
- License
- Score (nominal)
- 140
- Additional fields
- Indeksowana w: Web of Science, Scopus
- Uniform Resource Identifier
- https://cris.pk.edu.pl/info/article/CUT0c7d4f44abbe4a919138bf5acc3e13e1/
- URN
urn:pkr-prod:CUT0c7d4f44abbe4a919138bf5acc3e13e1
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