Applications of the olefin metathesis reaction

APPLICATIONS OF THE OLEFIN METATHESIS REACTION TO INDUSTRIAL PROCESSES... 

This overview has given industrial applications of the olefin metathesis reaction. If most commercial applications have been listed, only some of the non-commercialized ones were given but even so some conclusions can be drawn ... 

Streck, R. (1982) Some applications of the olefin metathesis reaction to polymer synthesis, J. Mol. Catal. 15, 3-19. 

Similar to the first edition of this Handbook, contributions have been arranged into three volumes. Volume I (Anna Wenzel, coeditor) emphasizes recent catalyst developments and mechanism and is intended to provide a foundation for the applications discussed throughout the rest of the Handbook. Volume 11 (Dan O Leary, coeditor) covers synthetic applications of the olefin metathesis reaction, and polymer chemistry is the topic of Volume III (Ezat Khosravi, coeditor). Chapter topics have been selected to provide comprehensive coverage of these... 

Recifeiolide has been prepared from cyclononanone the generality of this approach depends mainly on the availability of the starting ketone. A full discussion on the preparation of macrolides by intramolecular cyclizations involving 7r-allyl palladium complexes has appeared, together with some preliminary notes on the application of the olefin metathesis reaction to macrolide preparation. Yields for this latter process can be as high as ca. 60% under high dilution conditions. 

Preparative-scale olefin metathesis of hept-3-ene, to give a mixture of hexene (14%), heptene (38%), and octene (20%), is described by Sammes and Matlin, using the tungsten hexachloride-lithium aluminium hydride reagent." Other synthetic applications of the olefin metathesis reaction have also been reported" " and reviewed." ... 

Applications of the olefin metathesis reversible chemical reaction, discovered by Phillips Petroleum in the 1960s, were also developed in the subsequent years. By this reaction, Arco produces propylene from ethylene and butene-2 Hercules prepares its plastic, Metton, from dicyclopentadiene and Shell synthesizes its C12-C14 SHOP (Shell Higher Olefin Process) alcohols used for detergents. 

Perhaps the most basic form of the olefin metathesis reaction is the cross metathesis (CM) of acyclic olefins to yield new acyclic olefins (Fig. 4.11). The ratio of CM products may be controlled by steric and electronic factors to provide one product preferentially, rather than a statistical mixture, which is key to the synthetic utility of this reaction. For example, various functionalized olefins, dimers with bioactive substituents, and trisubstituted olefins have all been made by CM [33], and one of the industrial applications is the synthesis of insect pheromones [34]. 

Rouhi, A. Maureen. Olefin Metathesis Big-Deal Reaction. Chemical Engineering News 80 (December 23, 2002) 29-33 Olefin Metathesis The Early Days. Chemical Engineering News 80 (December 23, 2002) 34—38. These two brief articles explain the complex history of the discovery of the olefin metathesis reaction as well as its applications. 

A special application of bimetallic ruthenium complexes was found in the olefin metathesis reaction vide infra) The two metal centers were closely attached to one another through /r-halide anions. The labile assembly was the key feature to the formation of highly active catalysts. 

The olefin metathesis reaction has been proven to be an extremely useful tool for carbon-carbon bond formation in organic synthesis. Owing to the prevalence of this reaction in the synthetic organic literature, it is not surprising that it has been translated to the solid phase. Several metathesis catalysts, for example, A-C, have been developed and employed on the solid support for various applications (Figure 6.1)." Moreover, in several examples, the solid support affords a mechanism for the differentiation of the olefins, allowing the rapid removal of undesirable side products. 

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