On the question of zwitterionic intermediates in the [3+2] cycloaddition reactions between aryl azides and ethyl propiolate
Authors:
- Ewa Dresler,
- Przemysław Woliński,
- Aneta Wróblewska,
- Radomir Jasiński
Abstract
The molecular mechanism of the [3+2] cycloaddition reactions between aryl azides and ethyl propiolate was evaluated in the framework of the Molecular Electron Density Theory. It was found that independently of the nature of the substituent within the azide molecule, the cycloaddition process is realized via a polar but single-step mechanism. All attempts of localization as postulated earlier by Abu-Orabi and coworkers’ zwitterionic intermediates were not successful. At the same time, the formation of zwitterions with an “extended” conformation is possible on parallel reaction paths. The ELF analysis shows that the studied cycloaddition reaction leading to the 1,4-triazole proceeds by a two-stage one-step mechanism. It also revealed that both zwitterions are created by the donation of the nitrogen atom’s nonbonding electron densities to carbon atoms of ethyl propiolate.
- Record ID
- CUT86444fcc27df463c8648861e14c22952
- Publication categories
- ;
- Author
- Journal series
- Molecules, ISSN , e-ISSN 1420-3049, Biweekly
- Issue year
- 2023
- Vol
- 28
- No
- 24
- Pages
- [1-23]
- Article number
- 8152
- Other elements of collation
- rys.; schem.; tab.; Bibliografia (na s.) - 20-23; Bibliografia (liczba pozycji) - 74; Oznaczenie streszczenia - Abstr.; Numeracja w czasopiśmie - Vol. 28, Iss. 24
- Substantive notes
- This article belongs to the Special Issue: Synthesis, Functionalization and Applications of Nitrogen-Containing Compounds
- Keywords in English
- cycloaddition, azides, MEDT
- ASJC Classification
- DOI
- DOI:10.3390/molecules28248152 Opening in a new tab
- URL
- https://www.mdpi.com/1420-3049/28/24/8152 Opening in a new tab
- Language
- eng (en) English
- License
- Score (nominal)
- 140
- Score source
- journalList
- Score
- Publication indicators
- Uniform Resource Identifier
- https://cris.pk.edu.pl/info/article/CUT86444fcc27df463c8648861e14c22952/
- URN
urn:pkr-prod:CUT86444fcc27df463c8648861e14c22952
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