Unveiling the reactivity of cyclic azomethine ylides in [3+2] cycloaddition reactions within the Molecular Electron Density Theory
Authors:
- Luis R. Domingo,
- Karolina Kula,
- Mar Ríos-Gutiérrez
Abstract
The [3+2] cycloaddition (32CA) reactions of cyclic azomethine ylides with a series of acetylene derivatives have been studied within the Molecular Electron Density Theory (MEDT). Analysis of the Conceptual DFT indices allows the characterisation of the ambiphilic character of these cyclic AYs, thus participating as strong electrophiles and strong nucleophiles in polar 32CA reactions. The activation enthalpies associated with the 32CA reactions of these cyclic AYs are found in reasonable agreement with the experimental outcomes. These reactions proceed through a one‐step mechanism. The 32CA reactions with 1‐dimethylamino‐1‐propyne and dimethyl acetylenedicarboxylate take place through highly asynchronous polar transition states (TSs). On the other hand, the strain present in cyclooctyne allows explaining its participation in a non‐polar 32CA reaction via a synchronous TS. The present MEDT study allows establishing that the substitution in these cyclic AYs changes their parent pseudodiradical‐type reactivity to the zwitterionic‐type one.
- Record ID
- CUT52b4d2d234974c0f99ea5ec327019148
- Publication categories
- ;
- Author
- Journal series
- European Journal of Organic Chemistry, ISSN 1434-193X, e-ISSN 1099-0690, [1099-0690]
- Issue year
- 2020
- Vol
- 2020
- No
- 37
- Pages
- 5938-5948
- Other elements of collation
- rys.; schem.; tab.; Bibliografia (na s.) - 5947-5948; Bibliografia (liczba pozycji) - 24; Oznaczenie streszczenia - Abstr.; Numeracja w czasopiśmie - Vol. 2020, Iss. 37
- Keywords in English
- cyclic azomethine ylides, acetylene derivatives, [3+2] cycloaddition, Molecular Electron Density Theory, reactivity
- DOI
- DOI:10.1002/ejoc.202000745 Opening in a new tab
- URL
- https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/ejoc.202000745 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/CUT52b4d2d234974c0f99ea5ec327019148/
- URN
urn:pkr-prod:CUT52b4d2d234974c0f99ea5ec327019148
* 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.