Understanding the participation of fluorinated azomethine ylides in carbenoid-type [3 + 2] cycloaddition reactions with ynal systems: a molecular electron density theory study
Authors:
- Luis R. Domingo,
- Karolina Kula,
- Mar Ríos-Gutiérrez,
- Radomir Jasiński
Abstract
The carbenoid-type (cb-type) 32CA reaction of 1,1-difluoroated azomethine ylide (DFAY) with phenylpropynal has been studied using the molecular electron density theory (MEDT). Electron localization function (ELF) characterizes DFAY as a carbenoid species participating in cb-type 32CA reactions. The supernucleophilic character of DFAY and the strong electrophilic character of the ynal cause this polar 32CA reaction to have an unappreciable barrier; the reaction, which is highly exothermic, presents total chemo- and regioselectivity. ELF topological analysis of the bonding changes along the reaction establishes its non-concerted two-stage one-step mechanism, in which the nucleophilic attack of the carbenoid carbon of DFAY on the electrophilic carbonyl carbon of the ynal characterizes the cb-type reactivity of this three-atom component (TAC). The presence of two fluorines at DFAY modifies the pseudodiradical structure and reactivity of the simplest azomethine ylide to that of a carbenoid TAC participating in cb-type 32CA reactions toward electrophilic ethylenes.
- Record ID
- CUT383ec8686ea6407d85bd17c6d0d3f708
- Publication categories
- ;
- Author
- Journal series
- Journal of Organic Chemistry, ISSN 0022-3263, e-ISSN 1520-6904
- Issue year
- 2021
- Vol
- 86
- No
- 18
- Pages
- 12644-12653
- Other elements of collation
- rys.; schem.; tab.; Bibliografia (na s.) - 12651-12653; Bibliografia (liczba pozycji) - 66; Oznaczenie streszczenia - Abstr.; Numeracja w czasopiśmie - Vol. 86, Iss. 18
- Substantive notes
- Associated Content: Supporting Information
- Keywords in English
- cycloaddition, ylides, MEDT
- DOI
- DOI:10.1021/acs.joc.1c01126 Opening in a new tab
- URL
- https://pubs.acs.org/doi/10.1021/acs.joc.1c01126 Opening in a new tab
- Language
- eng (en) English
- Score (nominal)
- 140
- Additional fields
- Indeksowana w: Scopus
- Uniform Resource Identifier
- https://cris.pk.edu.pl/info/article/CUT383ec8686ea6407d85bd17c6d0d3f708/
- URN
urn:pkr-prod:CUT383ec8686ea6407d85bd17c6d0d3f708
* 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.