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Studies on the Mechanism of Intermolecular Enyne Metathesis: Kinetic Method and Alkyne Substituent Effects

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Brandon R. Galan, Anthony J. Giessert, Jerome B. Keister,* and Steven T. Diver*

Department of Chemistry, University at Buffalo, the State University of New York, Buffalo, New York 14260-3000

J. Am. Chem. Soc., 2005, 127 (16), pp 5762–5763

DOI: 10.1021/ja050174m

Publication Date (Web): March 30, 2005

Section:

Physical Organic Chemistry

Abstract

The kinetics of enyne metathesis were studied by IR spectroscopy for a variety of alkyne−alkene combinations. The rate law was determined for alkyne−ethylene and alkyne−1-hexene cross metathesis. In the cases examined, greater substitution on the alkyne accelerates the rate of metathesis, and chelation by propargylic esters was ruled out through rate comparison with hydrocarbon alkynes. The findings are discussed in terms of an alkylidene-first reaction mechanism, phosphine-bound ruthenium carbene resting states, and the rate-determining turnover of vinyl carbene intermediates (for alkyne−1-hexene metatheses).

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This article has been cited by 20 ACS Journal articles (5 most recent appear below).

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Mechanism of Intermolecular Ene-yne Metathesis Promoted by the Grubbs First-Generation Catalyst: An Alternative Entry Point to Catalysis
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  The kinetics of intermolecular alkene−alkyne (ene-yne) metathesis promoted by the first generation Grubbs catalyst (Cy3P)2Cl2Ru═CHPh (1) were investigated. The dissociated tricyclohexylphosphine plays an important kinetic role during the initial exchange ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Quantitative Catalyst−Substrate Association Relationships between Metathesis Molybdenum or Ruthenium Carbene Complexes and Their Substrates
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Journal of the American Chemical Society2010 132 (34), 12027-12033
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  Herein we present the long-sought quantitative catalyst−substrate association relationships based on experimentally measured quantitative association preferences of diverse metathesis Mo and Ru catalysts (Mo-1, Schrock Mo; Mo-2, Schrock−Hoveyda Mo; Ru-1, ...
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Initiation and Termination Mode of Enyne Cross-Metathesis and Metallotropic [1,3]-Shift Controlled by Remote Substituents
Sang Young Yun, Kung-Pern Wang, Mansuk Kim and Daesung Lee
Journal of the American Chemical Society2010 132 (26), 8840-8841
- Initiation and Termination Mode of Enyne Cross-Metathesis and Metallotropic [1,3]-Shift Controlled by Remote Substituents
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  The cross-metathesis of terminal alkyne and alkene using Ru-based Grubbs catalyst generally undergoes α-insertion. In this study, excellent control over α- and β-insertion of ruthenium alkylidene into terminal alkynes has been achieved by using a ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links