Industrial applications of homogeneous

In contrast to heterogeneous catalysis, industrial applications of homogeneous catalysis are relatively scarce, largely being restricted to the speciality and pharmaceutical sectors. Homogeneous catalysts have been well researched, since their catalytic centres can be relatively easily... 

A. Mortreux and F. Petit (eds.) Industrial Applications of Homogeneous Catalaysis. 

A. F. Noels, A.J. Hubert. In A. Mon-treux, F. Petit (Eds.), Industrial Applications of Homogeneous Catalysis. Riedel Publishing Company, Dordrecht, Netherlands, 1988. 

As already mentioned, the most important industrial application of homogeneous hydrogenation catalysts is for the enantioselective synthesis of chiral compounds. Today, not only pharmaceuticals and vitamins [3], agrochemicals [4], flavors and fragrances [5] but also functional materials [6, 7] are increasingly produced as enantiomerically pure compounds. The reason for this development is the often superior performance of the pure enantiomers and/or that regulations demand the evaluation of both enantiomers of a biologically active compound before its approval. This trend has made the economical enantioselective synthesis of chiral performance chemicals a very important topic. 

The cost of the catalysts represents a major hurdle on the road to the industrial application of homogeneous catalysis, and in particular for the production of fine chemicals [1, 2], This is particularly true for chiral catalysts that are based on expensive metals, such as rhodium, iridium, ruthenium and palladium, and on chiral ligands that are prepared by lengthy total syntheses, which often makes them more expensive than the metals. In spite of this, the number of large-scale applications for these catalysts is growing. Clearly, these can only be economic if the substrate catalyst ratio (SCR) can be very high, often between 103 and 105. 

SCHEME 5. Industrial applications of homogeneous asymmetric catalysis. 

I. Gauthier-Lafaye and R. Perron, in Industrial Applications of Homogeneous Catalysis (Eds. A. Mortreux and F. Petit), Chap. 2, D. Reidel Publ. Co., Dodrecht, 1988. 

This book has grown out of a graduate-level course on homogeneous catalysis that one of us taught at Northwestern University several times in the recent past. It deals with an interdisciplinary area of chemistry that offers challenging research problems. Industrial applications of homogeneous catalysis are proven, and a much wider application in the future is anticipated. Numerous publications and patent applications testify to the fact that in both the academic and industrial research laboratories the growth in research activity in this area in the past decade or so has been phenomenal. 

Interestingly, carbonylation of acetylene to give A A (eq. (1)) was among the first large-scale industrial applications of homogeneous catalysis by organometal-lic complexes (cf. Section 2.3.2.1). 

A. Behr, Industrial Application of Homogeneous Catalysis (Eds. A. Mortreux,... 

The catalytic addition of CO and H2 (synthesis gas) to olefins (hydroformylation or oxo-synthesis) is one of the major industrial applications of homogeneous catalysis. Over 6 million metric tons of aldehydes or alcohols (oxo-products) are produced worldwide per year. Commodities based on the C4 oxygenates currently have... 

The most important industrial application of homogeneous catalysts is the oxidation of hydrocarbons with oxygen or peroxides. Mechanistically, a distinction is made between ... 

From a historical perspective, the Monsanto process for the preparation of (l.)-DOPA in 1974 laid the foundation stone for industrial enantioselective catalysis. Since then it has been joined by a number of other asymmetric methods, such as enantioselective Sharpless epoxidation (glycidol (ARCO) and disparlure (Baker)), and cyclopropanation (cilastatin (Merck, Sumitomo) and pyre-throids (Sumitomo)). Nevertheless, besides the enantioselective hydrogenation of an imine for the production of (S)-metolachlor(a herbicide from Syngenta), the Takasago process for the production of (-)-menthol remains since 1984 as the largest worldwide industrial application of homogeneous asymmetric catalysis. [124]... 

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