Metathesis reaction catalysis

To date a number of reactions have been carried out in ionic liquids [for examples, see Dell Anna et al. J Chem Soc, Chem Commun 434 2002 Nara, Harjani and Salunkhe Tetrahedron Lett 43 1127 2002 Semeril et al. J Chem Soc Chem Commun 146 2002 Buijsman, van Vuuren and Sterrenburg Org Lett 3 3785 2007]. These include Diels-Alder reactions, transition-metal mediated catalysis, e.g. Heck and Suzuki coupling reactions, and olefin metathesis reactions. An example of ionic liquid acceleration of reactions carried out on solid phase is given by Revell and Ganesan [Org Lett 4 3071 2002]. 

In scrutinizing the various proposed reaction sequences in Eq. (26), one may classify the behavior of carbene complexes toward olefins according to four intimately related considerations (a) relative reactivities of various types of olefins (b) the polar nature of the metal-carbene bond (c) the option of prior coordination of olefin to the transition metal, or direct interaction with the carbene carbon and (d) steric factors, including effects arising from ligands on the transition metal as well as substituents on the olefinic and carbene carbons. Information related to these various influences is by no means exhaustive at this point. Consequently, some apparent contradictions exist which seem to cast doubt on the relevance of various model compound studies to conventional catalysis of the metathesis reaction, a process which unfortunately involves species which elude direct structural determination. 

Carbenes are both reactive intermediates and ligands in catalysis. They occur as intermediates in the alkene metathesis reaction (Chapter 16) and the cyclopropanation of alkenes. As intermediates they carry hydrogen and carbon substituents and belong therefore to the class of Schrock carbenes. As ligands they contain nitrogen substituents and are clearly Fischer carbenes. They have received a great deal of attention in the last decade as ligands in catalytic metal complexes [58], but the structural motive was already explored in the early seventies [59],... 

Numerous catalysts and metathesis reactions have been reported and it is not possible to do justice to all authors, not even to those who have contributed to the development of the mechanistic proofs summarised above. In Figure 16.9 we have collected a schematic overview of the type of reactions that are usually distinguished in metathesis catalysis. 

In laboratory-scale homogeneous catalysis applications, in the last decade further investigations have been carried out in which a less soluble organo-metallic catalyst system was utilized for metathesis reactions [46]. Under RCM-conditions, it was possible to convert substrates with functional groups that were problematic due to their potential to inactivate the rutheniiun catalyst here, the conversion in supercritical carbon dioxide avoids the protection of critical amino groups as an additional synthetic step. Consequently, it was possible to synthesize a number of carbo- and heterocyclic products with varying ring size (C4 to Cie). 

Alfassi, Z. B., and Benson, S. W., A simple empirical method for the estimation of activation energies in radical molecule metathesis reactions, Int. J. Chem. Kinetics S, 879 (1973). Allara, D. L., and Edelson, D., A computational analysis of a chemical switch mechanism. Catalysis-inhibition effects in a copper surface-catalyzed oxidation, J. Phys. Chem. 81, 2443 (1977). 

The first catalysis of an olefin metathesis reaction was reported by Banks and Bailey in 1964 (56). They reported that activated molybdenum hexacarbonyl on alumina converted propylene, for example, into ethylene and 2-butene at 150°C and 30 atm. Oxides of rhenium are also powerful heterogeneous catalysts. 

The first homogeneous catalysis of an olefin metathesis reaction... 

The ring-closing metathesis reaction has also been applied to the formation of a seven-membered cyclic sulfonamide C1999TL4761 >. Thus, heating 27 at reflux in dichloromethane (DCM) with ruthenium catalysis (Grubbs I catalyst) gave 28 in high yield (Equation 5). 

The wide range covered by nearly forty contributions ensures a concise overview of the latest developments in the field, w hethcr they be new methods of C-C bond formation or race-mization, asymmetric phase-transfer catalysis or stereoselective metathesis reactions, solid phase reactions or particularly elegant syntheses of challenging natural products. 

This volume provides the reader with the most important and exiting results pertaining the use of NHC complexes in transition-metal catalysis. Following an introductory chapter, which deals with the properties of NHC compounds and discusses some insightful examples, routes to NHC complexes will be described, a prerequisite for doing catalysis. Chapters on NHC complexes in oxidation chemistry and in metathesis reactions are accompanied by a chapter on palladium-catalyzed reactions and another on catalysis by other metals. Finally, this book would be incomplete without treating applications in asymmetric catalysis, which rounds out this volume. 

Asymmetric Synthesis by Homogeneous Catalysis Metal Vapor Synthesis of Transition Metal Compounds Metathesis Polymerization Processes by Homogeneous Catalysis Oligomerization Polymerization by Homogeneous Catalysis Organic Synthesis Using Metal-mediated Metathesis Reactions Titanium Inorganic Coordination Chemistry. 

---