Understanding the uniqueness of the stepwise [4 + 1] cycloaddition reaction between conjugated nitroalkenes and electrophilic carbene systems with a molecular electron density theory perspective
Authors:
- Agnieszka Kącka-Zych
Abstract
The [4 + 1] cycloaddition (41CA) and [2 + 1] cycloaddition (21CA) reactions of the α‐halogeno‐nitroalkenes with carbene have been studied using the molecular electron density theory through density functional theory calculations at the MPWB1K(PCM)/6‐311G(d,p) computational level. The 41CA reaction take place through a polar two‐step mechanism involving the formation of a zwitterionic intermediate. The competitive 21CA reaction path proceeds according to nonconcerted two‐stage one‐step. Bonding evolution theory analysis of 41CA reaction allows the distinguishing of four groups along the reaction path. The reaction begins with rupture of the C–C double bond of the alkene moiety and formation of the pseudoradical center. Formation of the O–C and C–C new single bonds begins in subsequent phases. In the last stage of the 41CA reaction path, we observed the formation of an N–C new double bond. In the case of 21CA reaction path, we observed the successive rupture of the C–C double bond of the alkene moiety, formation of C–C new single bond and pseudoradical center, and creation of a second C–C single bond.
- Record ID
- CUTd5c7da938ec545f29843cad82b310304
- Publication categories
- ;
- Author
- Journal series
- International Journal of Quantum Chemistry, ISSN 0020-7608, e-ISSN 1097-461X
- Issue year
- 2021
- Vol
- 121
- No
- 2
- Pages
- [1-14]
- Article number
- e26440
- Other elements of collation
- schem.; tab.; Bibliografia (na s.) - 13-14; Bibliografia (liczba pozycji) - 55; Oznaczenie streszczenia - Abstr.; Data udostępnienia on-line - 2020-08-24; Numeracja w czasopiśmie - Vol. 121, Iss. 2
- Keywords in English
- [2+1] cycloaddition reaction, [4+1] cycloaddition reaction, bonding evolution theory, carbene precursor, molecular electron density theory
- DOI
- DOI:10.1002/qua.26440 Opening in a new tab
- URL
- https://onlinelibrary.wiley.com/doi/10.1002/qua.26440 Opening in a new tab
- Language
- eng (en) English
- Score (nominal)
- 70
- Additional fields
- Indeksowana w: Web of Science, Scopus
- Uniform Resource Identifier
- https://cris.pk.edu.pl/info/article/CUTd5c7da938ec545f29843cad82b310304/
- URN
urn:pkr-prod:CUTd5c7da938ec545f29843cad82b310304
* 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.