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Fast-Initiating, Ruthenium-based Catalysts for Improved Activity in Highly E-Selective Cross Metathesis

Ahmed, Tonia S. and Grubbs, Robert H. (2017) Fast-Initiating, Ruthenium-based Catalysts for Improved Activity in Highly E-Selective Cross Metathesis. Journal of the American Chemical Society, 139 (4). pp. 1532-1537. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170126-110542342

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Abstract

Ruthenium-based olefin metathesis catalysts bearing dithiolate ligands have been recently employed to generate olefins with high E-selectivity (>99% E) but have been limited by low to moderate yields. In this report, ^1H NMR studies reveal that a major contributing factor to this low activity is the extremely low initiation rates of these catalysts with trans olefins. Introducing a 2-isopropoxy-3-phenylbenzylidene ligand in place of the conventional 2-isopropoxybenzylidene ligand resulted in catalysts that initiate rapidly under reaction conditions. As a result, reactions were completed in significantly less time and delivered higher yields than those in previous reports while maintaining high stereoselectivity (>99% E).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jacs.6b11330DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jacs.6b11330PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jacs.6b11330PublisherSupporting Information
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2017 American Chemical Society. Received: October 31, 2016; Publication Date (Web): January 20, 2017. We acknowledge funding from the Office of Naval Research (N00014-14-1-0650) and the NSF (CHE-1502616). T.S.A. is grateful for support from the National Science Foundation through a Graduate Research Fellowship. Any opinion, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. Materia, Inc. is thanked for generous donations of catalysts 2a and 3a. M. A. Pribisko, B. L. Quigley, and R. M. B. Silva are thanked for their input on this manuscript. J. R. Sampson, W. J. Wolf, N. F. Nathel, and T. P. Montgomery are thanked for helpful discussions. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Office of Naval Research (ONR)N00014-14-1-0650
NSFCHE-1502616
NSF Graduate Research FellowshipUNSPECIFIED
Issue or Number:4
Record Number:CaltechAUTHORS:20170126-110542342
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170126-110542342
Official Citation:Fast-Initiating, Ruthenium-based Catalysts for Improved Activity in Highly E-Selective Cross Metathesis Tonia S. Ahmed and Robert H. Grubbs Journal of the American Chemical Society 2017 139 (4), 1532-1537 DOI: 10.1021/jacs.6b11330
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:73754
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:26 Jan 2017 19:47
Last Modified:03 Oct 2019 16:31

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