Improved Ruthenium Catalysts for Z-Selective Olefin Metathesis
Abstract
Several new C–H-activated ruthenium catalysts for Z-selective olefin metathesis have been synthesized. Both the carboxylate ligand and the aryl group of the N-heterocyclic carbene have been altered and the resulting catalysts evaluated using a range of metathesis reactions. Substitution of bidentate with monodentate X-type ligands led to a severe attenuation of metathesis activity and selectivity, while minor differences were observed between bidentate ligands within the same family (e.g., carboxylates). The use of nitrato-type ligands in place of carboxylates afforded a significant improvement in metathesis activity and selectivity. With these catalysts, turnover numbers approaching 1000 were possible for a variety of cross-metathesis reactions, including the synthesis of industrially relevant products.
Additional Information
© 2011 American Chemical Society. Received: October 31, 2011. Publication Date (Web): November 19, 2011. Lawrence Henling and Dr. Michael Day are acknowledged for X-ray crystallographic analysis. Dr. David VanderVelde is thanked for assistance with NMR experimentation and analysis. This work was financially supported by the NIH (NIH 5R01GM031332-27), the NSF (CHE-1048404), Mitsui Chemicals, Inc. (K.E.), and the NDSEG (fellowship to B.K.K.). Instrumentation on which this work was carried out were supported by the NSF (X-ray diffractometer, CHE-0639094) and the NIH (NMR spectrometer, RR027690). Materia, Inc. is thanked for its donation of metathesis catalysts.Attached Files
Accepted Version - nihms343610.pdf
Supplemental Material - ja210225e_si_001.pdf
Supplemental Material - ja210225e_si_002.cif
Files
Additional details
- PMCID
- PMC3257350
- Eprint ID
- 29947
- Resolver ID
- CaltechAUTHORS:20120403-082650298
- NIH
- 5R01GM031332-27
- NSF
- CHE-1048404
- Mitsui Chemicals, Inc.
- National Defense Science and Engineering Graduate (NDSEG) Fellowship
- NSF
- CHE-0639094
- NIH
- RR027690
- Materia, Inc.
- Created
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2012-04-03Created from EPrint's datestamp field
- Updated
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2021-11-09Created from EPrint's last_modified field