Olefin metathesis industrial application

Although olefin metathesis had soon after its discovery attracted considerable interest in industrial chemistry, polymer chemistry and, due to the fact that transition metal carbene species are involved, organometallic chemistry, the reaction was hardly used in organic synthesis for many years. This situation changed when the first structurally defined and stable carbene complexes with high activity in olefin metathesis reactions were described in the late 1980s and early 1990s. A selection of precatalysts discovered in this period and representative applications are summarized in Table 1. 

Further important industrial applications of olefin metathesis include the synthesis of 3,3-dimethyl-l-butene ( neohexene , intermediate for the production of musk perfume) from ethene and 2,4,4-trimethyl-2-pentene, the manufacture of a,co-dienes from ethene and cycloalkenes (reversed RCM), and the ROMP of cyclooctene and norbomene to Vestenamer and Norsorex , respectively. 

Because of the importance of olefin metathesis in the industrial production of olefins and polymers, many different catalysts have been developed. Almost all of these are transition metal-derived, some rare exceptions being EtAlCl2 [758], Me4Sn/Al203 [759], and irradiated silica [760]. The majority of catalytic systems are based on tungsten, molybdenum, and rhenium, but titanium-, tantalum-, ruthenium-, osmium-, and iridium-based catalysts have also proven useful for many applications. 

The treatment of equivalent amounts of two different alkenes with a metathesis catalyst generally leads to the formation of complex product mixtures [925,926]. There are, however, several ways in which cross metathesis can be rendered synthetically useful. One example of an industrial application of cross metathesis is the ethenolysis of internal alkenes. In this process cyclic or linear olefins are treated with ethylene at 50 bar/20 80 °C in the presence of a heterogeneous metathesis catalyst. The reverse reaction of ADMET/RCM occurs, and terminal alkenes are obtained. 

Olefin metathesis chemistry has had a profound impact in several areas of chemical research, including organome-tallics, polymer chemistry, and small molecule synthesis,many of which have industrial applications. For example, CM is currently utilized in the commercial preparation of several agrochemicals, polymer and fuel additives, and pharmacophores. Unlike RCM reactions, which are typically conducted under dilute... 

In general, there are three modes of olefin metathesis ring closing metathesis (RCM),M ring opening metathesis polymerization (ROMP),5-6 and cross metathesis (CM).7-9 Although all three have industrial applications, the main use of olefin metathesis for fine chemicals production lies in the modes of CM and RCM (Scheme 28.1). 

In just a short time, olefin metathesis has become an important tool to the synthetic organic chemist. The large-scale use of this chemistry has already been seen in the polymer and fragrance industries. As drug candidates move through the development pipeline, the commercial application of this chemistry probably will be put into practice. The applications of the asymmetric catalysts allow for an efficient coupling of two reactions with the same catalyst and reaction conditions. 

Olefin metathesis has become one of the most important large-scale technical processes for the manufacture of olefins in the petrochemical industry [123]. When cyclic olefins are used as substrates, high-molecular polymers, which are formed by the so-called ring-opening metathesis (ROM), have found applications as elastomers and plastics. Gas-phase studies on the mechanism of olefin metathesis had been confined to simple metal carbenes, for example [Mn=CH2]+, [Fe=CH2]+,and [Co=CH2]+ [124-127]. Most of the metatheses have been observed with deuterated ethylene. 

Carbene species can be stabilized by complexation to metals and transferred to olefinic substrates in catalytic reactions. Although the main industrial application of carbenes is in metathesis (Chapter 6), an important application in the area of fine chemicals is to asymmetric cyclopropanation. 

Banks, R.L. (1984) Olefin metathesis technology and application, in Applied Industrial Catalysi (ed. B.E. Leach), Academic Press, New York, p. 215. 

Other potential industrial applications of olefin metathesis, including the... 

R. L. Banks takes up the subject of olefin metathesis previously discussed by J. J. Rooney and A. Stewart in Volume 1 and gives an authorative review of the very substantial literature which has appeared in the last four years. Naturally his account covers both heterogeneous and homogeneous catalysis and he summarizes as well the industrial applications which have been made to date of metathesis reactions. S. Malinowski and J. Kijeriski review the specialist field of very highly basic catalysts largely developed by the work of the Polish school. In their chapter they discuss the evidence for the nature of catalysts such as alkali-treated magnesium and other oxides and the kind of reactions that take place thereon. J. M. Winterbottom in a chapter with emphasis on the literature since 1973 concentrates mainly on the dehydration of alcohols as the fundamental studies on dehydration far exceed those on hydration, which features mainly in the patent literature. His chapter dis-... 

The metathesis reactions of cycloalkenes are discussed in detail in Ch. 11-14 and their cross-metathesis reactions with acyclic olefins in Ch. 15. Degradation reactions of unsaturated polymers by olefin metathesis are covered in Ch. 16. Industrial applications are described in Ch. 17. 

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]. 

Technology for a number of applications of olefin metathesis has been developed (, fO At Phillips, potential processes for producing isoamylenes for polyisoprene synthesis and long-chain linear olefins from propylene have been through pilot plant development. In the area of specialty petrochemicals, potential industrial applications include the preparation of numerous olefins and diolefins. High selectivities can be achieved by selection of catalyst and process conditions. The development of new classes of catalysts allows the metathesis of certain functional olefins (, 14). The metathesis of alkynes is also feasible (15) ... 

If more than one molecular fragment is substituted, this is categorized as a metathesis. A recent industrial application is the olefin metathesis to produce e.g. Propene from Ethene and 2-Butene. ... 

Mol, J. Industrial applications of olefin metathesis. Journal of Molecular Catalysis A Chemical, 213(l) 39-45, 2004. 

---