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

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• 作者：Selina C. Wang ; Dawn M. Troast ; Martin Conda-Sheridan ; Gang Zuo ; Donna LaGarde ; Janis Louie ; Dean J. Tantillo
• 刊名：Journal of Organic Chemistry
• 出版年：2009
• 出版时间：October 16, 2009
• 年：2009
• 卷：74
• 期：20
• 页码：7822-7833
• 全文大小：1203K
• 年卷期：v.74,no.20(October 16, 2009)
• ISSN：1520-6904

文摘

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.