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Published September 23, 2013 | Supplemental Material + Accepted Version
Journal Article Open

Investigations into Ruthenium Metathesis Catalysts with Six-Membered Chelating NHC Ligands: Relationship between Catalyst Structure and Stereoselectivity


A series of ruthenium catalysts bearing five-membered chelating NHC architectures that exhibit very high Z-selectivity in a variety of metathesis reactions have recently been reported. It was envisioned that catalysts possessing six-membered chelates could similarly exhibit high Z-selectivity and address limitations of this methodology. We thus prepared a number of new catalysts and systematically investigated the impact of the NHC and anionic ligand on their stereoselectivity. In standard metathesis assays, only catalysts containing six-membered chelated NHC structures and η^2-bound anionic ligands favored the Z-olefin products. In addition, substitution with bulkier N-aryl groups led to improved Z-selectivity. The effect of ligand structure on stereoselectivity discovered in this study will be useful in the future design of highly active and Z-selective ruthenium catalysts.

Additional Information

© 2013 American Chemical Society. Received: July 15, 2013; Published: August 29, 2013. We thank Dr. D. Benitez, Dr. B. K. Keitz, and Dr. P. Teo for helpful discussions and suggestions for this work. Materia, Inc. is thanked for the generous donation of catalysts. Dr. M. W. Day and Mr. L. M. Henling are acknowledged for X-ray crystallography analysis. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology, CHE-0639094. This work was financially supported by National Institutes of Health (NIH 5R01GM031332-27) and Mitsui Chemicals, Inc.

Attached Files

Accepted Version - nihms520329.pdf

Supplemental Material - om4006966_si_001.pdf

Supplemental Material - om4006966_si_002.cif

Supplemental Material - om4006966_si_003.cif

Supplemental Material - om4006966_si_004.cif

Supplemental Material - om4006966_si_005.cif

Supplemental Material - om4006966_si_006.cif

Supplemental Material - om4006966_si_007.cif

Supplemental Material - om4006966_si_008.cif


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