Mechanistic Insights into the DABCO-Catalyzed Cloke-Wilson Rearrangement: A DFT Perspective.
Journal
The Journal of organic chemistry
ISSN: 1520-6904
Titre abrégé: J Org Chem
Pays: United States
ID NLM: 2985193R
Informations de publication
Date de publication:
17 Nov 2023
17 Nov 2023
Historique:
medline:
27
10
2023
pubmed:
27
10
2023
entrez:
27
10
2023
Statut:
ppublish
Résumé
The mechanism and selectivity patterns of the DABCO-catalyzed Cloke-Wilson rearrangement were computationally studied in detail using density functional theory calculations. Our computations suggest that the process occurs stepwise involving the initial ring opening of the cyclopropane promoted by a DABCO molecule followed by a ring-closure reaction of the readily formed zwitterionic intermediate. The regioselectivity of the initial nucleophilic ring-opening step strongly depends on the nature of the substituent attached to the cyclopropane moiety. The physical factors governing the preference for the more sterically hindered C2 (tertiary) position have been quantitatively analyzed by applying the combined activation strain model-energy decomposition analysis method. In addition, our calculations revealed a new mechanism for the analogous transformation involving vinylcyclopropanes consisting of an initial S
Identifiants
pubmed: 37885222
doi: 10.1021/acs.joc.3c02011
pmc: PMC10661052
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
15902-15912Références
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