Homogeneous catalysis organic transformation

For most applications, enzymes are purified after isolation from various types of organisms and microorganisms. Unfortunately, for process application, they are then usually quite unstable and highly sensitive to reaction conditions, which results in their short operational hfetimes. Moreover, while used in chemical transformations performed in water, most enzymes operate under homogeneous catalysis conditions and, as a rule, cannot be recovered in the active form from reaction mixtures for reuse. A common approach to overcome these limitations is based on immobilization of enzymes on solid supports. As a result of such an operation, heterogeneous biocatalysts, both for the aqueous and nonaqueous procedures, are obtained. 

Liquid multiphasic systems, where one of the phases is catalyst-philic, are attractive for organic transformation, as they provide built-in methods of catalyst separation and product recovery, as well as advantages of catalytic efficiency. The present chapter focuses on recent developments of catalyst-philic phases used in conjunction with heterogeneous catalysts. Interest in this field is fueled by the desire to combine the high catalytic efficiency typical of homogeneous catalysis with the easy product-catalyst separation features provided by heterogeneous catalysis and in situ phase separations. 

Phase transfer catalysis (1,2) has become in recent years a widely used, well-established synthetic technique applied with advantage to a multitude of organic transformations. In addition to a steadily increasing number of reports in the primary literature, there are several reviews (3-6), comprehensive monographs (7-10) and an ACS Audio Course (1 ) which describe the phase transfer process and which provide extensive compilations of phase transfer agents and reaction types. While the list of applications and in many cases the synthetic results are impressive, phase transfer catalysts (PTCs) suffer some of the same disadvantages as more conventional hetero-and homogeneous catalysts — separation and... 

Certain classical coordination complexes (see Coordination Complexes) of iron (e.g. Prussian blue) will be dealt with in other articles (see Iron Inorganic Coordination Chemistry and Cyanide Complexes of the Transition Metals), as will much of the chemistries of iron carbonyls (see Metal Carbonyls) and iron hydrides (see Hydrides) (see Carbonyl Complexes of the Transition Metals Transition Metal Carbonyls Infrared Spectra, and Hydride Complexes of the Transition Metals). The use of organoiron complexes as catalysts (see Catalysis) in organic transformations will be mentioned but will primarily be covered elsewhere (see Asymmetric Synthesis by Homogeneous Catalysis, and Organic Synthesis using Transition Metal Carbonyl Complexes). 

Triphenylphosphine complexes of Ru, Rh, and Pd continue to play a crucial role in homogeneous catalysis for a wide range of transformations. Palladium complexes with PPh3 are extremely useful in organic synthesis.112,113... 

Fluorous biphasic catalysis is another active area in multiphasic homogeneous catalysis. The term fluorous was introduced [90] as the analogue to the term aqueous, to emphasize the fact that one of the phases of a biphase system is richer in fluorocarbons than the other. Fluorous biphase systems can be used in catalytic chemical transformations by immobilizing catalysts in the fluorous phase. A fluorous catalyst system consists of a fluorous phase containing a preferentially fluorous-soluble catalyst and a second product phase, which may be any organic or inorganic solvent with limited solubility in the fluorous phase (Figure 2.8a). 

Environmental Chemical Catalysis. Catalysis in a single phase is normally referred to as homogeneous catalysis, while catalysis that takes place n< l he interface of two phases is classified as heterogeneous catalysis. In environmental systems, several categories of catalyzed reactions play an mipoi Umt role in the transformation of inorganic and organic chemical species. 

Homogeneous catalysis has revolutionized the art of organic synthesis. It is now challenging to find a synthesis of any complex molecular target that does not rely on at least one, if not many, transition metal-mediated or catalyzed steps. Why have these transformations achieved such privileged status In many cases, metal-catalyzed reactions open avenues to new methods unknown in traditional organic chemistry or impart levels of selectivity, especially enanti-oselectivity, that allow more atom economical syntheses of many valuable products. 

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