Handbook of Metathesis

Robert H. Grubbs received his Ph.D. from Columbia University for work with Ron Breslow. After a postdoctoral year with Jim Collman at Stanford University, he joined the faculty at Michigan State University. In 1978, he moved to the California Institute of Technology, where he is now the Victor and Elizabeth Atkins Professor of Chemistry. Among many other awards, he received the Nobel Prize in 2005 for his research on the metathesis reaction. His research interests include polymer chemistry, organometallic catalysis, and the development of new synthetic organic methodology. Anna G. Wenzel received her PhD at Harvard University under the guidance of Prof. E. N. Jacobsen. From 2003 to 2006, she joined the group of Prof. R. H. Grubbs as an NIH Postdoctoral Scholar. In 2006, she joined the faculty as an Assistant Professor at the W. M. Keck Science Department in Claremont, California. In 2012, she was promoted to Associate Professor. Her research topics are asymmetric catalysis, organometallic chemistry, and organic synthesis.

Preface

HIGH-OXIDATION ON STATE MOLYBDENUM AND TUNGSTEN COMPLEXES RELEVANT TO OLEFIN METATHESIS
Introduction
New Imido Ligands and Synthetic Approaches
Bispyrrolide and Related Complexes
Monoalkoxide Pyrrolide (MAP) Complexes
Reactions of Alkylidenes with Olefins
Olefin and Metallacyclopentane Complexes
Tungsten Oxo Complexes
Bisaryloxides
Other Constructs
Conclusions

ALKANE METATHESIS
Introduction
Alkane Metathesis by Single-Catalyst Systems
Alkane Metathesis by Tandem, Dual-Catalytic Systems
Conclusion

DIASTEREOCONTROL IN OLEFIN METATHESIS: THE DEVELOPMENT OF Z-SELECTIVE RUTHENIUM CATAYLSTS
Introduction
The Challenge of Z-Selective Olefin Metathesis
Previous Strategies
A Serendipitous Discovery
Catalyst Studies
Applications of Z-Selective Ru Metathesis Catalysts
Conclusion

RUTHENIUM OLEFIN METATHESIS CATALYSTS SUPPORTED BY CYCLIC ALKYL AMINOCARBENES (CAACs)
Introduction
Properties and Preparation of CAAC Ligands
CAAC-Supported, Ruthenium Olefin Metathesis Catalysts
Summary

SUPPORTED CATALYSTS AND NONTRADITIONAL REACTION MEDIA
Introduction
Supported Catalyst Systems
Olefin Metathesis in Nontraditional Media
Conclusions

INSIGHTS FROM COMPUTATIONAL STUDIES ON d0 METAL-CATALYZED ALKENE AND ALKYNE METATHESIS AND RELATED REACTIONS
Introduction
Alkene Metathesis
Alkyne Metathesis
Alkane Metathesis
Outlook

COMPUTATIONAL STUDIES OF RUTHENIUM-CATALYZED OLEFIN METATHESIS
Introduction
Computational Investigations of Non-Chelated Ruthenium Catalysts
Computational Investigations of Chelated, Z-Selective Ruthenium Catalysts
Accuray of the Computational Methods

INTERMEDIATES IN OLEFIN METATHESIS
Introduction
Metathesis-Active, Early-Metal Metallacycles
Intermediates in Ruthenium-Catalyzed Olefin Metathesis
Future Directions

FACTORS AFFECTING INITIATION RATES
Introduction
Grubbs Second-Generation Catalyst
Grubbs-Hoveyda-Type Precatalysts
Pyridine Solvates
Piers Catalysts
Indenylidene Carbene Precatalysts
Z-Selective Catalysts
Herrmann-Type, BisNHCs
Conclusions

DEGENERATE METATHESIS
Introduction
Degenerate Metathesis Mechanisms
Degenerate Metathesis with Early Transition-Metal Catalysts
Degenerate Metathesis with Ruthenium Catalysts
Beneficial Effects of Degenerate Metathesis
Conclusions

MECHANISMS OF OLEFIN METATHESIS CATALYST DECOMPOSITION AND METHODS OF CATALYST REACTIVATION
Introduction
Decomposition of Mo and W Imido Alkylidene Catalysts and Related Complexes
Decomposition of Ru Alkylidene Catalysts and Related Complexes
Conclusions

SOLVENT AND ADDITIVE EFFECTS ON OLEFIN METATHESIS
General Introduction
Solvent Effects on Olefin Metathesis
Additive Effects on Olefin Metathesis
Summary

METATHESIS PRODUCT PURIFICATION
Introduction
Chromatographic and Chemical Removal of Ruthenium
Removal by Complexation
Conclusion

RUTHENIUM INDENYLIDENE CATALYSTS FOR ALKENE METATHESIS
Introduction
The Initial Development of Indenylidene Metal Complexes for Alkene Metathesis
Binuclear Indenylidene Ruthenium Catalysts Arising from Ruthenium(arene) Complexes
Preparation of Ruthenium Indenylidene Catalysts from RuCl2(PPh3)3
Ruthenium Catalysts Bearing a Chelating Indenylidene Ligand
Conclusion