Mechanism of the Ni(0)-Catalyzed Vinylcyclopropane−Cyclopentene Rearrangement

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 elim...

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Bibliographic Details
Published in:Journal of organic chemistry 2009-10, Vol.74 (20), p.7822-7833
Main Authors: Wang, Selina C, Troast, Dawn M, Conda-Sheridan, Martin, Zuo, Gang, LaGarde, Donna, Louie, Janis, Tantillo, Dean J
Format: Article
Language:English
Subjects:
Catalysis
Cyclopentanes - chemistry
Cyclopropanes - chemistry
Molecular Structure
Nickel - chemistry
Vinyl Compounds - chemistry
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Summary: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo901525u