Experimental and computational studies on stepwise [3+2]- cycloadditions of diaryldiazomethanes with electron-deficient dimethyl ( E )- and ( Z )-2,3-dicyanobutenedioates
Authors:
- Grzegorz Mlostoń,
- Małgorzata Celeda,
- Radomir Jasiński,
- Heinz Heimgartner
Abstract
Electron-deficient dimethyl ( E )- and ( Z )-2,3-dicyanobutenedioates (dimethyl dicyanofumarate and dicyanomaleate, respectively) react with diaryldiazomethanes at room temperature under spontaneous evolution of N 2 . The type of the products strongly depends on the structure of the diazo compound. Whereas diphenyldiazomethane and its bis(4-methoxy) derivative yield cyclopropanes, sterically crowded 5-diazo-5 H -dibenzo[a, d]cycloheptane derivatives afford either the dimer of the carbene formed via N 2 elimination or the adduct of the carbene onto the starting diazo compound. The course of the studied reactions is rationalized by stepwise mechanisms initiated by the formation of a C–N bond. A cascade of reactions leads to the corresponding cyclopropanes or to release of a carbene species. The formation of a pyrazole via [3+2]-cycloaddition (32CA) is observed only in reactions with (trimethylsilyl)diazomethane, which behaves similar to the parent diazomethane. The proposed mechanisms were analyzed computationally using the DFT method.
- Record ID
- CUT6ed142ff25c745f9852a0ca7f67716e5
- Publication categories
- ;
- Author
- Journal series
- European Journal of Organic Chemistry, ISSN 1434-193X, e-ISSN 1099-0690, [1099-0690]
- Issue year
- 2019
- No
- 2-3
- Pages
- 422-431
- Other elements of collation
- schem.; tab.; Bibliografia (na s.) - 430-431; Bibliografia (liczba pozycji) - 41; Oznaczenie streszczenia - Abstr.; Numeracja w czasopiśmie - Iss. 2-3
- Substantive notes
- Special issue: Organic Reaction Mechanisms
- Keywords in English
- cycloaddition, mechanism, diazocompounds
- DOI
- DOI:10.1002/ejoc.201800837 Opening in a new tab
- URL
- https://onlinelibrary.wiley.com/doi/full/10.1002/ejoc.201800837 Opening in a new tab
- Language
- eng (en) English
- Score (nominal)
- 70
- Additional fields
- Indeksowana w: Scopus
- Uniform Resource Identifier
- https://cris.pk.edu.pl/info/article/CUT6ed142ff25c745f9852a0ca7f67716e5/
- URN
urn:pkr-prod:CUT6ed142ff25c745f9852a0ca7f67716e5
* 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.