The participation of 3,3,3-trichloro-1-nitroprop-1-ene in the [3+2] cycloaddition reaction with selected nitrile N-oxides in the light of the experimental and MEDT quantum chemical study
Authors:
- Karolina Zawadzińska,
- Mar Ríos-Gutiérrez,
- Karolina Kula,
- Przemysław Woliński,
- Barbara Mirosław,
- Tomasz Krawczyk,
- Radomir Jasiński
Abstract
The regioselective zw-type [3 + 2] cycloaddition (32CA) reactions of a series of aryl-substituted nitrile N-oxides (NOs) with trichloronitropropene (TNP) have been both experimentally and theoretically studied within the Molecular Electron Density Theory (MEDT). Zwitterionic NOs behave as moderate nucleophiles while TNP acts as a very strong electrophile in these polar 32CA reactions of forward electron density flux, which present moderate activation Gibbs free energies of 22.8–25.6 kcal·mol−1 and an exergonic character of 28.4 kcal·mol−1 that makes them irreversible and kinetically controlled. The most favorable reaction is that involving the most nucleophilic MeO-substituted NO. Despite Parr functions correctly predicting the experimental regioselectivity with the most favorable O-CCCl3 interaction, these reactions follow a two-stage one-step mechanism in which formation of the O-C(CCl3) bond takes place once the C-C(NO2) bond is already formed. The present MEDT concludes that the reactivity differences in the series of NOs come from their different nucleophilic activation and polar character of the reactions, rather than any mechanistic feature.
- Record ID
- CUT329ba9dae1034fdea0e59b1f5334d5d4
- Publication categories
- ;
- Author
- Journal series
- Molecules, ISSN , e-ISSN 1420-3049, Biweekly
- Issue year
- 2021
- Vol
- 26
- No
- 22
- Pages
- [1-19]
- Article number
- 6774
- Other elements of collation
- schem.; tab.; wykr.; Bibliografia (na s.) - 15-19; Bibliografia (liczba pozycji) - 90; Oznaczenie streszczenia - Abstr.; Numeracja w czasopiśmie - Vol. 26, Iss. 22, Spec. Iss.
- Substantive notes
- Special Issue: Huisgen 3+n Dipolar Cycloaddition Reactions: An Accessible and Useful Tool in Modern Organic and Heterocycle Synthesis
- Keywords in English
- [3+2] cycloaddition, nitrile oxides, nitroalkenes, reactivity, molecular mechanism, molecular electron density theory
- DOI
- DOI:10.3390/molecules26226774 Opening in a new tab
- URL
- https://www.mdpi.com/1420-3049/26/22/6774 Opening in a new tab
- Related project
- Wyposażenie laboratoriów Wydziałów Biologii i Biotechnologii, Matematyki, Fizyki i Informatyki oraz Wydziału Chemii pod kątem badań substancji o aktywności biologicznej i próbek środowiskowych. . Project leader at PK: , ,
- 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/CUT329ba9dae1034fdea0e59b1f5334d5d4/
- URN
urn:pkr-prod:CUT329ba9dae1034fdea0e59b1f5334d5d4
* presented citation count is obtained through Internet information analysis, and it is close to the number calculated by the Publish or PerishOpening in a new tab system.