Mechanistic Studies on N-Heterocyclic Carbene-Catalyzed Umpolung of ß,γ-Unsaturated α-Diketones.
J Org Chem
; 86(6): 4432-4439, 2021 Mar 19.
Article
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| MEDLINE
| ID: mdl-33719444
ABSTRACT
The mechanism of N-heterocyclic carbene-catalyzed umpolung of ß,γ-unsaturated α-diketone was studied using both density functional theory (DFT) calculations and experimental methods. In contrast to the originally proposed mechanism, the calculations revealed a more complicated process involving both nucleophilic O-acylated homoenolate and electrophilic α,ß-unsaturated acyl azolium intermediates. The experimental studies confirmed the existence of the aforementioned two key intermediates. A revised mechanism has been proposed to demonstrate the detailed mechanistic insights into the product formation.
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
J Org Chem
Año:
2021
Tipo del documento:
Article
País de afiliación:
China