Handbook of Metathesis
Description
Edited by the Nobel laureate R. H. Grubbs and A. G. Wenzel, this volume 1 of the 3-volume work focusses on catalyst development and mechanism. With a list of contributors that reads like a "Who's-Who" of metathesis, this is an indispensable one-stop reference for chemists in academia and industry.
Other available volumes:
Volume 2: Applications in Organic Synthesis, Editors: R. H. Grubbs and D. J. O´Leary
Volume 3: Polymer Synthesis, Editors: R. H. Grubbs and E. Khosravi
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Other editions
Additional editions
Persons
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.
Content
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
Chapter 1
High-Oxidation State Molybdenum and Tungsten Complexes Relevant to Olefin Metathesis
Richard R. Schrock
1.1 Introduction
The first examples of high-oxidation state ("d0") alkylidene and alkylidyne complexes (of tantalum) were published in 1974 and 1975 [1]. Several years of research were required to show that the principles behind tantalum chemistry could be employed to prepare alkylidene and alkylidyne complexes of Mo, W, and Re in their highest oxidation states (counting the alkylidene as a dianionic ligand and the alkylidyne as a trianionic ligand), and that these high-oxidation state complexes, especially those that contain one or more alkoxide ligands, are efficient catalysts for alkene and alkyne metathesis reactions, respectively. This process has been described in previous reviews [2]. Applications of high-oxidation state catalysts for alkene and alkyne metathesis in organic chemistry have also been reviewed [3], although each of these subjects is reviewed again elsewhere in this series in view of the many recent advancements.
This review will focus on isolated and characterized high-oxidation state molybdenum and tungsten alkylidene and metallacyclobutane complexes. Attention will be directed largely toward monoalkoxide pyrrolide (MAP) complexes because they have yielded the majority of new results in the last several years. MAP species have been found to be especially efficient in several Z-selective olefin metathesis reactions, such as homocoupling, cross-coupling, ethenolysis, and ROMP (see Grubbs, Handbook of Metathesis, 2nd Edition, Volume 2, Chapter 7). Most of what is presented here has appeared since a review in 2009 [4].
In the last decade, impressive advances have been made in the synthesis of alkylidene and alkylidyne complexes that contain metals from groups 4 [5] and 5 [5]i,j,m, [6], especially Ti and V, but - except for the ROMP of norbornene by vanadium complexes - group 4 and 5 metals have not shown wide-ranging activity for olefin metathesis. Well-characterized rhenium(VII) complexes are known to be active for metathesis, and many rhenium(VII) alkylidene and alkylidyne complexes have been isolated [2]a, but little attention has been paid to the syntheses of rhenium alkylidene or alkylidyne complexes in the last decade. Theoretical calculations have been carried out on M(X)(CHR´)(Y)(Z) complexes and their reactions with olefins, where X is imido (primarily) or oxo, and Y and Z are monoanionic ligands [7]; the results of these calculations are discussed in Chapter 6. Basic principles of Mo and W olefin metathesis catalysts will be discussed only if the new data have shed light on the basics. Advances in attaching Mo or W catalysts to solid supports, such as silica [8], alumina [9], or organic polymers [10], will also not be reviewed here, as it is discussed in Chapter 5. Transferring the knowledge gained from the studies of homogeneous catalysts to the synthesis of supported catalysts, especially those in which specificity is retained, is one of the remaining challenges in the field.
Table 1.1, located at the end of this chapter, provides a ready reference to Mo and W compounds that have been prepared since about 2007 that are relevant to olefin metathesis studies. Abbreviations can be found in the footnote to Table 1.1. Some entries in Table 1.1 are not discussed in the text since they have not been central to recent olefin metathesis studies. X-ray structures (indicated with an asterisk (*) in Table 1.1) will not be described in detail unless some unusual features warrant discussion.
Table 1.1 Tabulation of Isolated Neutral Alkylidene Complexes
Mo(NR)(CHR´)X2 (X = pyrrolide, indolide, or pyrazolide) References Mo(NAr)(CHR´)(Pyr)2 R´ = t-Bu or CMe2Ph [11] Mo(N-2,6-Br2-4-MeC6H2)(CH-t-Bu)(Pyr)2 [11] Mo(NAd)(CHCMe2Ph)(Pyr)2 [11] Mo(NAd)(CHCMe2Ph)(Pyr)2(PMe3)* [12] Mo(NR)(CHCMe2Ph)(Pyr)2(bipy) R = Ar*, Ad, ArMe2, ArCl, AriPr, ArtBu, ArMes [55] Mo(NAr)(CHCMe2Ph)X2 X = Me4Pyr*, i-Pr2Pyr*, Ph2Pyr*, Indolide* [12] Mo(NAr)(CH-t-Bu)(Ph2Pyr)2 [12] Mo(NAr)(CHCMe2Ph)(indolide)2(THF) [12] Mo(NAr)(CHCMe2Ph)(R2Pz)2 R2Pz = 3,5-diphenylpyrazolide* or 3,5-di-t-butylpyrazolide [8]g Mo(NR)(CHCMe2Ph)(Me2Pyr)2 R = Ar, ArMe2, ArCF3 [13] Mo(NAd)(CHCMe2Ph)(Me2Pyr)2* [12] Mo(NAr)(CH-t-Bu)(Me2Pyr)2 [14] Mo(NAr)(CHCMe2Ph)(MesPyr)2* [15] Mo(NAd)(CH-t-Bu)(MesPyr)2 [16] Mo(NAd)(CHCMe2Ph)(indolide)2 [12] Mo(NAd)(CHCMe2Ph)(MesPyr)2 [17] Mo(NAd)(CHCMe2Ph)(2-CNPyr)2* [17] Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)2 [18] Mo(NArX)(CHCMe2Ph)(Me2Pyr)2 X = Cl, i-Pr, Mes* [19] Mo(NArX)(CH-t-Bu)(Me2Pyr)2 X = CF3, t-Bu, Trip [19] Mo(NArMes2)(CHCMe2Ph)(Me2pyr)2 [20] Mo(NArMes2)(CHCMe2Ph)(Pyr)2(py) [21] Mo(NR)(CHR´)(pyrrolide)(OR?) (Mo MAP) Mo(NAr)(CHCMe2Ph)(X)(ORF6) X = Me4Pyr, i-Pr2Pyr, Ph2Pyr [12] Mo(NAr)(CHCMe2Ph)(X)(ORF6)(PMe3) X = Me2Pyr, Me4Pyr, i-Pr2Pyr, Ph2Pyr* [12] Mo(NAr)(CHCMe2Ph)(Me2Pyr)(OR?) OR? = O-t-Bu, OCHMe2, OAr,*OCH(CF3)2, ORF6 [22] Mo(NAr)(CHCMe2Ph)(Me2Pyr)(OR?) OR? = OTPP*, ODPP*, ORF6* [23] Mo(NAr)(CHCMe2Ph)(Me2Pyr)(OR?) OR? = O-1-PhC6H10, OSi(O-t-Bu)3, OSiPh3 [24] Mo(NAr)(CHCMe2Ph)(Me2Pyr)(OSiPh3) [25] (R)-Mo(NAr)(CHCMe2Ph)(Me2Pyr)(OBr2Bitet)* [26] (R)-Mo(NAr)(CHCMe2Ph)(Me2Pyr)(OBr2Bitet)(PMe3)* [27] (S)-Mo(NAr)(CHCMe2Ph)(Me2Pyr)(OBr2Bitet)* [26] Mo(NAr)(CH2)(Pyr)(OHIPT)* [28] Mo(NAr)(CH2)(Me2Pyr)(OTPP) [36] Mo(NAr)(CHCMe2Ph)(Pyr)(OTPP) [29] Mo(NAr)(CHCMe2Ph)(Pyr)[OSi(t-Bu)3]* [30] Mo(NAr)(CHCMe2Ph)(Me2Pyr)(OCPh3) [31] Mo(NAr)(CHCMe2Ph)(Pyr)(OR) OR = ODPPPh* or ODPPiPr* [32] Mo(NAd)(CHCMe2Ph)(Pyr)(OR) OR = ODPPPh or ODPPiPr [32] Mo(NAd)(CHCMe2Ph)(Me2Pyr)(OR) OR = ODPPPh or ODPPiPr [32] Mo(NAd)(CHCMe2Ph)(Me2Pyr)(OTPP) [33] Mo(NAd)(CHCMe2Ph)(Pyr)(OHIPT) [34] Mo(NAd)(CH-t-Bu)(Pyr)(OHIPT) [34] Mo(NAd)(CHCMe2Ph)(Pyr)(OR) OR = O-(3,5-R´2C6H3)2C6H3 (R´ = Me or t-Bu), OCPh3, OSiTMS3 [31] Mo(NAd)(CH-t-Bu)(Pyr)(OHIPT)* [28] Mo(NAd)(CHCMe2Ph)(MesPyr)(OR) OR = OTPP*, OBr2Bitet*, OHIPT* [17] Mo(NAd)(CHCMe2Ph)(CNPyr)(OHIPT)* [17] Mo(NAd)(CHCMe2Ph)(Pyr)(OHMT) [35] Mo(NArMe2)(CHCMe2Ph)(Pyr)(OHIPT) [14] Mo(NR)(CHCMe2Ph)(Pyr)(OHMT) R = Ar, ArMe2, ArCl, AriPr*, ArtBu, ArMes [55] Mo(NArX)(CHCMe2Ph)(Me2Pyr)(OHMT) X = Cl, i-Pr, Mes* [19] Mo(NArX)(CH-t-Bu)(Me2Pyr)(OHMT) X = CF3, t-Bu,...