Chemical shifts reported were internally referenced to residual chloroform. Analyses were performed between NaC1 plates neat or with chloroform as a solvent. Purity of compounds and reaction conversions were determined on either a Hewlett-Packard HPA gas chromatograph using a capillary column with a flame ionization detector or on silica coated tic plates with mixtures of pentane and ethyl acetate as the mobile phase.
The three volumes are edited by the Nobel laureate Professor Robert H. Grubbs California Institute of Technology, USA in collaboration with an impressive panel of co-editors, all famous experts in the field. Since the first edition several books, thematic issues and extensive reviews on metathesis reactions have appeared 2 — 8 and this new edition enormously adds to the present knowledge, representing the most important compendium of the state-of-the-art of alkene, alkane and alkyne metathesis and metathesis polymerisation, with a strong focus on the present research in this fascinating field of chemistry.
Metathesis has real potential for large scale valorisation in many industrial areas in the near future. Schrock Massachusetts Institute of Technology, USA authoritatively and attractively surveys high oxidation state molybdenum and tungsten complexes relevant to olefin metathesis.
Special attention is paid to the synthesis of novel imido ligands, bispyrrolide and related complexes, and to the appealing applications of monoalkoxide pyrrolide MAP complexes which are highly efficient in Z-selective olefin metathesis reactions homocoupling, cross-coupling, ethenolysis and ring-opening metathesis polymerisation ROMP.
The rich information offers deep insights into the mechanism and stereochemistry of metathesis reactions initiated by high oxidation state Mo and W complexes that have played a crucial role in the development of olefin metathesis chemistry.
The potential for producing supported metal-alkylidene catalysts of Mo, Ta, W and their applications in alkane metathesis is fully illustrated.
Keitz California Institute of Technology gives an interesting account of diastereocontrol in olefin metathesis when using Z-selective ruthenium catalysts.
This chapter concentrates on the fulminant development of Ru-based Z-selective metathesis catalysts as well as on a fresh mechanistic grasp specifically concerning the effects of N-heterocyclic carbenes NHC and of their substituents on reaction stereoselectivity and catalyst decomposition. Catalyst preparation, characterisation and utilisation in RCM, CM, ethenolysis and degenerate metathesis are discussed.
A particular challenge for the evolution of this type of catalysts is evidenced, namely the implementation of CAAC ligands for stereospecific control in asymmetric olefin metathesis and regiospecificity in ring expansion metathesis polymerisation.
Chapter 5 by Daryl P. Allen Materia Inc, USA is dedicated to supported catalysts and non-traditional reaction media, both issues of intense contemporary research.
In the second part modern concepts of using non-traditional reaction media for example water, ionic liquids, fluorous systems are introduced. The assets of computational chemistry in terms of understanding at a molecular level and the recent advances in structure-reactivity relationships catalytic performance are revealed.
From another perspective Peng Liu, Buck L. Intermediates in the early and late transition metal-catalysed olefin metathesis, as investigated by X-ray crystallography and nuclear magnetic resonance NMR spectroscopy, are examined by Anna G.
Wenzel in Chapter 8. New Insights on Olefin Metatheses How initiation rates play an essential role in olefin metatheses induced by Grubbs, Hoveyda-Grubbs, Piers and Herrmann catalysts or by indenylidene-Ru precatalysts is enticingly portrayed in Chapter 9 by Justin R.
Griffiths and Steven T. A detailed analysis of the main factors affecting the initial rates such as ligand dissociation and exchange, alkene coordination, and the nature of the catalyst and solvent is given.
In the next chapter, the intriguing topic of degenerate metathesis reactions as promoted by heterogeneous and homogeneous, early- and late-transition metal catalytic systems, is reviewed by Ian C.
In order to obtain conclusive evidence on the mechanism of methylene exchange process, some selected metathesis reactions are screened using various isotopic-labelling experiments, in addition to pertinent stereochemical studies.
In Chapter 11, Yann Schrodi California State University, Northridge, USA considers the most significant aspects of the mechanism of catalyst decomposition in olefin metathesis as well as specific methods for catalyst reactivation. Along these lines, the decomposition mechanisms of very active and stereoselective Mo- and W-imido alkylidene complexes are elaborated followed by a report on the decomposition pathways of numerous classes of Ru-alkylidene complexes.
The information provided indicates different behaviour in the thermal decomposition for the first and second generation catalysts, particularly for Ru-alkylidene complexes.
Critical observations on catalyst stability, nature of intermediates and products of catalyst decomposition are advanced. The decomposition mechanism in the presence of functional groups or small molecules is also discussed. Strategies for preventing catalyst decomposition and for extending catalyst life i.
The crucial role played by the solvent and additives on catalyst activity and selectivity is thoroughly documented by Shawn K. Collins University of Montreal, Canada in Chapter Examples include the effects of perfluoroaromatic solvents or additives such as alcohols that increase the initiation rates of metathesis reactions induced by Ru-based catalysts.
In enyne metathesis promoted by Ru catalysts, the author convincingly shows that both activity and selectivity are strongly influenced when changing the reaction atmosphere from nitrogen to ethylene. In numerous asymmetric metathesis reactions the reactivity and enantioselectivity can be strongly determined by halide salts in numerous asymmetric metathesis reactions.
Additives of the Lewis-acid type frequently promote macrocyclisations whereas other types of acid or base additives suppress olefin isomerisation favouring metathesis.All Mechanisms: Displaying mechanisms: Alicyclic- electrophilic addition of bromine to cyclohexene (bromonium ion opening) Alicyclic- Grobb rearrangement.
OLEFIN METATHESIS Olefin metathesis, or alkene metathesis, is an important process in petroleum refining and in the synthesis of important compounds such as pharmaceuticals. The mechanism of olefin metathesis is related to pericyclic reactions like Diels Alder and [2+2] reactions.
In other words, it occurs through the concerted interaction of. The blog All Things Metathesis has a nice entry about a large scale metathesis reaction, and how the changing economy has impacted it.
Metathesis can be (over)simply stated as moving double bonds around.
The reaction is actually a combination of breaking and reforming the double bonds, but from looking strictly at the inputs and outputs, it looks like the double bonds are moving around. His life’s work drifted down this path thanks to a problem his team encountered when studying the mechanism of living metathesis polymerisation reactions.
To their dismay they found that no known catalysts worked for one of the reactions they wanted to look at. Metathesis is the exchange of atoms or functional groups in the substrates and the rearrangement of their matching partners to form new compounds.
Simple examples were well-studied in traditional . a common amino acid, and a cross metathesis dimerization mechanism was applied to eugenol.
Once these compounds had been synthesized, they were characterized using.