Insights into the mechanism and regiochemistry of the 1,3-dipolar cycloaddition reaction between benzaldehyde and diazomethane - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Theoretical Chemistry Accounts: Theory, Computation, and Modeling Année : 2020

Insights into the mechanism and regiochemistry of the 1,3-dipolar cycloaddition reaction between benzaldehyde and diazomethane

Résumé

The 1,3-dipolar cycloaddition reaction of benzaldehyde with diazomethane is investigated, in gas phase and in diverse polar solvents, using the molecular electron density theory through density functional theory calculations at the B3LYP(+D3)/6-31G(d) level. Analysis of the reaction pathway reveals that this reaction takes place along a concerted but asynchronous mechanism. Computations show that the acetophenone product is kinetically and thermodynamically more favored than 2-phenylacetaldehyde product in agreement with experimental outcomes. The favored cyclization mode and the observed regioselectivity of this cycloaddition are rationalized by both activation energy calculations, frontier molecular orbital analysis and reactivity indices. Also, polar solvents effect favors the reaction. Furthermore, we performed electron localization function (ELF) topological analysis. The ELF topological analysis of diazomethane indicates that this reactant presents an allenicpseudoradicalelectronic structure.
Fichier non déposé

Dates et versions

hal-02972139 , version 1 (20-10-2020)

Identifiants

Citer

K Abbiche, H Mohammad Salim, M Salah, N Mazoir, A Zeroual, et al.. Insights into the mechanism and regiochemistry of the 1,3-dipolar cycloaddition reaction between benzaldehyde and diazomethane. Theoretical Chemistry Accounts: Theory, Computation, and Modeling, 2020, 139 (9), 12p. ⟨10.1007/s00214-020-02662-4⟩. ⟨hal-02972139⟩
48 Consultations
0 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More