Inhibitory Effect of Ethylene in Ene-Yne Metathesis: The Case for Ruthenacyclobutane Resting States
Timothy M. Gregg, Jerome B. Keister and Steven T. Diver*
*Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000, United States, Email: diverbuffalo.edu
T. M. Gregg, J. B. Keister, S. T. Diver, J. Am. Chem. Soc., 2013, 135, 16777-16780.
DOI: 10.1021/ja4085012 (free Supporting Information)
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In reaction kinetics and mechanistic studies of ethylene-internal alkyne metathesis promoted by Piers's catalyst, an inverse effect of ethylene on the reaction rate was found. Kinetic and mechanistic studies identify a ruthenacyclobutane as resting state. Preparative syntheses of several 2,3-disubstituted 1,3-butadienes were achieved at low ethylene pressures.
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