Mechanism of the Ni(0)-catalyzed vinylcyclopropane-cyclopentene rearrangement.
J Org Chem
; 74(20): 7822-33, 2009 Oct 16.
Article
em En
| MEDLINE
| ID: mdl-19780523
ABSTRACT
A combination of physical organic experiments and quantum chemical calculations were used to construct a detailed mechanistic model for the Ni(0)-N-heterocyclic carbene-catalyzed vinylcyclopropane-cyclopentene rearrangement that involves a mutistep oxidative addition/haptotropic shift/reductive elimination pathway. No evidence for the intermediacy of radicals or zwitterions was found. The roles of substituents on the vinylcyclopropane substrate and variations in the ligands on Ni were evaluated. It is postulated that bulky carbene ligands facilitate formation of the active catalyst species.
Texto completo:
1
Base de dados:
MEDLINE
Assunto principal:
Compostos de Vinila
/
Ciclopentanos
/
Ciclopropanos
/
Níquel
Idioma:
En
Ano de publicação:
2009
Tipo de documento:
Article