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Studies on the mechanism of intermolecular enyne metathesis: kinetic method and alkyne substituent effects.
J Am Chem Soc. 2005 Apr 27; 127(16):5762-3.JA

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).

Authors+Show Affiliations

Galan BR
Department of Chemistry, University at Buffalo, the State University of New York, Buffalo, New York 14260-3000, USA.
Giessert AJ
No affiliation info available
Keister JB
No affiliation info available
Diver ST
No affiliation info available

MeSH

AlkenesAlkynesKineticsStructure-Activity Relationship

Pub Type(s)

Journal Article
Research Support, N.I.H., Extramural
Research Support, U.S. Gov't, Non-P.H.S.
Research Support, U.S. Gov't, P.H.S.

Language

eng

PubMed ID

15839654

Citation

Galan, Brandon R., et al. "Studies On the Mechanism of Intermolecular Enyne Metathesis: Kinetic Method and Alkyne Substituent Effects." Journal of the American Chemical Society, vol. 127, no. 16, 2005, pp. 5762-3.
Galan BR, Giessert AJ, Keister JB, et al. Studies on the mechanism of intermolecular enyne metathesis: kinetic method and alkyne substituent effects. J Am Chem Soc. 2005;127(16):5762-3.
Galan, B. R., Giessert, A. J., Keister, J. B., & Diver, S. T. (2005). Studies on the mechanism of intermolecular enyne metathesis: kinetic method and alkyne substituent effects. Journal of the American Chemical Society, 127(16), 5762-3.
Galan BR, et al. Studies On the Mechanism of Intermolecular Enyne Metathesis: Kinetic Method and Alkyne Substituent Effects. J Am Chem Soc. 2005 Apr 27;127(16):5762-3. PubMed PMID: 15839654.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Studies on the mechanism of intermolecular enyne metathesis: kinetic method and alkyne substituent effects. AU - Galan,Brandon R, AU - Giessert,Anthony J, AU - Keister,Jerome B, AU - Diver,Steven T, PY - 2005/4/21/pubmed PY - 2005/7/26/medline PY - 2005/4/21/entrez SP - 5762 EP - 3 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 127 IS - 16 N2 - 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). SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/15839654/Studies_on_the_mechanism_of_intermolecular_enyne_metathesis:_kinetic_method_and_alkyne_substituent_effects_ DB - PRIME DP - Unbound Medicine ER -