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Highly Selective Ruthenium Metathesis Catalysts for Ethenolysis

Thomas, Renee M. and Keitz, Benjamin K. and Champagne, Timothy M. and Grubbs, Robert H. (2011) Highly Selective Ruthenium Metathesis Catalysts for Ethenolysis. Journal of the American Chemical Society, 133 (19). pp. 7490-7496. ISSN 0002-7863. PMCID PMC3104465.

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N-Aryl,N-alkyl N-heterocyclic carbene (NHC) ruthenium metathesis catalysts are highly selective toward the ethenolysis of methyl oleate, giving selectivity as high as 95% for the kinetic ethenolysis products over the thermodynamic self-metathesis products. The examples described herein represent some of the most selective NHC-based ruthenium catalysts for ethenolysis reactions to date. Furthermore, many of these catalysts show unusual preference and stability toward propagation as a methylidene species and provide good yields and turnover numbers at relatively low catalyst loading (<500 ppm). A catalyst comparison showed that ruthenium complexes bearing sterically hindered NHC substituents afforded greater selectivity and stability and exhibited longer catalyst lifetime during reactions. Comparative analysis of the catalyst preference for kinetic versus thermodynamic product formation was achieved via evaluation of their steady-state conversion in the cross-metathesis reaction of terminal olefins. These results coincided with the observed ethenolysis selectivities, in which the more selective catalysts reach a steady state characterized by lower conversion to cross-metathesis products compared to less selective catalysts, which show higher conversion to cross-metathesis products.

Item Type:Article
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URLURL TypeDescription CentralArticle
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2011 American Chemical Society. Received: January 21, 2011. Published: April 21, 2011. This research was supported by the National Science Foundation through a Graduate Research Fellowship to R.M.T. B. K. K. acknowledges the NDSEG for a graduate fellowship. The authors acknowledge Drs. Lawrence Henling and Michael Day for obtaining the X-ray crystallographic structures of complexes 12 and 15. We thank the NSF (CHE-1048404) and NIH (5R01GM031332-Z7) for funding and Materia, Inc. for the gift of methyl oleate and catalysts 1, 2, and 4.
Funding AgencyGrant Number
NSF Graduate Research FellowshipCHE-1048404
National Defense Science and Engineering Graduate (NDSEG) FellowshipUNSPECIFIED
Issue or Number:19
PubMed Central ID:PMC3104465
Record Number:CaltechAUTHORS:20110608-084832814
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Official Citation:Highly Selective Ruthenium Metathesis Catalysts for Ethenolysis Renee M. Thomas, Benjamin K. Keitz, Timothy M. Champagne, Robert H. Grubbs Journal of the American Chemical Society 2011 133 (19), 7490-7496
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:23940
Deposited By: Tony Diaz
Deposited On:14 Jun 2011 17:23
Last Modified:03 Oct 2019 02:51

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