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 journalArticle

41 Citations (Scopus)

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 languageEnglish (US)
Pages (from-to)7822-7833
Number of pages12
JournalJournal of Organic Chemistry
Volume74
Issue number20
DOIs
StatePublished - Oct 16 2009

Fingerprint

Cyclopentanes
Ligands
Catalysts
Substrates
Experiments
carbene

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Wang, S. C., Troast, D. M., Conda-Sheridan, M., Zuo, G., LaGarde, D., Louie, J., & Tantillo, D. J. (2009). Mechanism of the Ni(0)-catalyzed vinylcyclopropane-cyclopentene rearrangement. Journal of Organic Chemistry, 74(20), 7822-7833. https://doi.org/10.1021/jo901525u

Mechanism of the Ni(0)-catalyzed vinylcyclopropane-cyclopentene rearrangement. / Wang, Selina C.; Troast, Dawn M.; Conda-Sheridan, Martin; Zuo, Gang; LaGarde, Donna; Louie, Janis; Tantillo, Dean J.

In: Journal of Organic Chemistry, Vol. 74, No. 20, 16.10.2009, p. 7822-7833.

Research output: Contribution to journalArticle

Wang, SC, Troast, DM, Conda-Sheridan, M, Zuo, G, LaGarde, D, Louie, J & Tantillo, DJ 2009, 'Mechanism of the Ni(0)-catalyzed vinylcyclopropane-cyclopentene rearrangement', Journal of Organic Chemistry, vol. 74, no. 20, pp. 7822-7833. https://doi.org/10.1021/jo901525u
Wang, Selina C. ; Troast, Dawn M. ; Conda-Sheridan, Martin ; Zuo, Gang ; LaGarde, Donna ; Louie, Janis ; Tantillo, Dean J. / Mechanism of the Ni(0)-catalyzed vinylcyclopropane-cyclopentene rearrangement. In: Journal of Organic Chemistry. 2009 ; Vol. 74, No. 20. pp. 7822-7833.
@article{b6fb5fae211b4ad5b8946a558a34b4da,
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.",
author = "Wang, {Selina C.} and Troast, {Dawn M.} and Martin Conda-Sheridan and Gang Zuo and Donna LaGarde and Janis Louie and Tantillo, {Dean J.}",
year = "2009",
month = "10",
day = "16",
doi = "10.1021/jo901525u",
language = "English (US)",
volume = "74",
pages = "7822--7833",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "20",

}

TY - JOUR

T1 - Mechanism of the Ni(0)-catalyzed vinylcyclopropane-cyclopentene rearrangement

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.

UR - http://www.scopus.com/inward/record.url?scp=70349849337&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=70349849337&partnerID=8YFLogxK

U2 - 10.1021/jo901525u

DO - 10.1021/jo901525u

M3 - Article

C2 - 19780523

AN - SCOPUS:70349849337

VL - 74

SP - 7822

EP - 7833

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 20

ER -