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Enantioselective Olefin Metathesis with Cyclometalated Ruthenium Complexes

Hartung, John and Dornan, Peter K. and Grubbs, Robert H. (2014) Enantioselective Olefin Metathesis with Cyclometalated Ruthenium Complexes. Journal of the American Chemical Society, 136 (37). pp. 13029-13037. ISSN 0002-7863. PMCID PMC4183615 . https://resolver.caltech.edu/CaltechAUTHORS:20140908-092755830

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Abstract

The success of enantioselective olefin metathesis relies on the design of enantioenriched alkylidene complexes capable of transferring stereochemical information from the catalyst structure to the reactants. Cyclometalation of the NHC ligand has proven to be a successful strategy to incorporate stereogenic atoms into the catalyst structure. Enantioenriched complexes incorporating this design element catalyze highly Z- and enantioselective asymmetric ring opening/cross metathesis (AROCM) of norbornenes and cyclobutenes, and the difference in ring strain between these two substrates leads to different propagating species in the catalytic cycle. Asymmetric ring closing metathesis (ARCM) of a challenging class of prochiral trienes has also been achieved. The extent of reversibility and effect of reaction setup was also explored. Finally, promising levels of enantioselectivity in an unprecedented Z-selective asymmetric cross metathesis (ACM) of a prochiral 1,4-diene was demonstrated.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://pubs.acs.org/doi/abs/10.1021/ja506611kPublisherArticle
http://dx.doi.org/10.1021/ja506611kDOIArticle
http://pubs.acs.org/doi/suppl/10.1021/ja506611kPublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4183615/PubMed CentralArticle
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: July 1, 2014. Publication Date (Web): August 19, 2014. The authors declare no competing financial interest. This work was financially supported by the NIH (5R01GM031332-27 to R.H.G.) and the NSF (CHE-1212767 to R.H.G.). Thanks to Mr. L. M. Henling for X-ray crystallography. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094). NMR spectra were obtained by instruments supported by the NIH (RR027690). Materia, Inc. is thanked for its donation of metathesis catalysts. Dr. Daryl Allen of Materia, Inc., Dr. Jeffrey Cannon, Zachary Wickens and Dr. Scott Virgil of the Caltech Center for Catalysis and Chemical Synthesis are thanked for helpful advice.
Funders:
Funding AgencyGrant Number
NIH5R01GM031332-27
NSFCHE-1212767
NSFCHE-0639094
NIHRR027690
Issue or Number:37
PubMed Central ID:PMC4183615
Record Number:CaltechAUTHORS:20140908-092755830
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20140908-092755830
Official Citation:Enantioselective Olefin Metathesis with Cyclometalated Ruthenium Complexes John Hartung, Peter K. Dornan, and Robert H. Grubbs Journal of the American Chemical Society 2014 136 (37), 13029-13037
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:49320
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:08 Sep 2014 16:47
Last Modified:03 Oct 2019 07:12

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