Mechanism of the Ni(0)-catalyzed vinylcyclopropane-cyclopentene rearrangement

Selina C. Wang; Dawn M. Troast; Martin Conda-Sheridan; Gang Zuo; Donna LaGarde; Janis Louie; Dean J. Tantillo

doi:10.1021/jo901525u

Mechanism of the Ni(0)-catalyzed vinylcyclopropane-cyclopentene rearrangement

Selina C. Wang, Dawn M. Troast, Martin Conda-Sheridan, Gang Zuo, Donna LaGarde, Janis Louie, Dean J. Tantillo

Research output: Contribution to journal › Article › peer-review

49 Scopus citations

Abstract

(Chemical Equation Presented) 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.

Original language	English (US)
Pages (from-to)	7822-7833
Number of pages	12
Journal	Journal of Organic Chemistry
Volume	74
Issue number	20
DOIs	https://doi.org/10.1021/jo901525u
State	Published - Oct 16 2009
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry

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title = "Mechanism of the Ni(0)-catalyzed vinylcyclopropane-cyclopentene rearrangement",

abstract = "(Chemical Equation Presented) 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.",

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AU - Wang, Selina C.

AU - Troast, Dawn M.

AU - Conda-Sheridan, Martin

AU - Zuo, Gang

AU - LaGarde, Donna

AU - Louie, Janis

AU - Tantillo, Dean J.

PY - 2009/10/16

Y1 - 2009/10/16

N2 - (Chemical Equation Presented) 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.

AB - (Chemical Equation Presented) 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.

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Mechanism of the Ni(0)-catalyzed vinylcyclopropane-cyclopentene rearrangement

Abstract

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