Transition Metal Catalyzed Oxidations

Transition-metal-catalyzed oxidations may or may not proceed via peroxocomplexes. Twelve important industrial organic oxidation processes catalyzed by transition metals, many of which probably involve peroxo intermediates, have been tabulated (88). Even when peroxo intermediates can be isolated from such systems, it does not necessarily foUow that these are tme intermediates in the main reaction. 

Modern variants are the enzyme-catalyzed and the transition-metal-catalyzed Baeyer-Villiger reaction, allowing for an oxidation under mild conditions in good yields, with one stereoisomer being formed predominantly in the enzymatic reaction ... 

Besides the oxidative and transition-metal-catalyzed condensation reactions discussed above, several other syntheses were developed to generate PPP and PPP derivatives. 

Oxidants Available for Selective Transition Metal-catalyzed Epoxidation... 

There are several available terminal oxidants for the transition metal-catalyzed epoxidation of olefins (Table 6.1). Typical oxidants compatible with most metal-based epoxidation systems are various alkyl hydroperoxides, hypochlorite, or iodo-sylbenzene. A problem associated with these oxidants is their low active oxygen content (Table 6.1), while there are further drawbacks with these oxidants from the point of view of the nature of the waste produced. Thus, from an environmental and economical perspective, molecular oxygen should be the preferred oxidant, because of its high active oxygen content and since no waste (or only water) is formed as a byproduct. One of the major limitations of the use of molecular oxygen as terminal oxidant for the formation of epoxides, however, is the poor product selectivity obtained in these processes [6]. Aerobic oxidations are often difficult to control and can sometimes result in combustion or in substrate overoxidation. In... 

Table 6.1 Oxidants used in transition metal-catalyzed epoxida-tions, and their active oxygen content.

Table 6.12 Transition metal-catalyzed epoxidation of olefins with H202 as terminal oxidant.

Olefin metathesis is the transition-metal-catalyzed inter- or intramolecular exchange of alkylidene units of alkenes. The metathesis of propene is the most simple example in the presence of a suitable catalyst, an equilibrium mixture of ethene, 2-butene, and unreacted propene is obtained (Eq. 1). This example illustrates one of the most important features of olefin metathesis its reversibility. The metathesis of propene was the first technical process exploiting the olefin metathesis reaction. It is known as the Phillips triolefin process and was run from 1966 till 1972 for the production of 2-butene (feedstock propene) and from 1985 for the production of propene (feedstock ethene and 2-butene, which is nowadays obtained by dimerization of ethene). Typical catalysts are oxides of tungsten, molybdenum or rhenium supported on silica or alumina [ 1 ]. 

To my knowledge, the first transition metal-catalyzed reaction utilizing S-S bond activation was reported by Holmquist el al. in 1960 [14]. The reaction of (PhS)2 with CO (950 atm) in the presence of chromium oxide on AI2O3 at 275°C furnished thioester 57 in 31% yield (Eq. 7.42). 

The discussion of the activation of bonds containing a group 15 element is continued in chapter five. D.K. Wicht and D.S. Glueck discuss the addition of phosphines, R2P-H, phosphites, (R0)2P(=0)H, and phosphine oxides R2P(=0)H to unsaturated substrates. Although the addition of P-H bonds can be sometimes achieved directly, the transition metal-catalyzed reaction is usually faster and may proceed with a different stereochemistry. As in hydrosilylations, palladium and platinum complexes are frequently employed as catalyst precursors for P-H additions to unsaturated hydrocarbons, but (chiral) lanthanide complexes were used with great success for the (enantioselective) addition to heteropolar double bond systems, such as aldehydes and imines whereby pharmaceutically valuable a-hydroxy or a-amino phosphonates were obtained efficiently. 

The oxidation of alcohols is an important reaction in organic chemistry. While this transformation is traditionally performed in organic solvents, the use of aqueous orgarric solutions has just recently become a field of intense study (1-6). The effect of water on transition metal-catalyzed reactions, however, remains widely unexplored as most of these reactions require dry organic solvents to avoid decomposition of the transition metal catalyst, of water sensitive reagents, and/or intermediates by a nucleophilic attack of water (1). Comparative studies focusing on the effect of water as a co-solvent on the catalyst and the proceedings of a reaction are therefore rare (7). 

Transition Metal-Catalyzed Epoxidation of Alkenes. Other transition metal oxidants can convert alkenes to epoxides. The most useful procedures involve f-butyl hydroperoxide as the stoichiometric oxidant in combination with vanadium or... 

Besides Wacker oxidation, other transition-metal catalyzed oxidations have also been carried out in aqueous medium. For example, methyl groups can be selectively hydroxylated by platinum salts in water.88 In this way, p-toluenesulfonic acid was oxidized to benzy-lic alcohol, which was subsequently oxidized into the aldehyde (Eq. 3.19).89... 

Warwel, S., Sojka, M., and Rusch, M. Synthesis of Dicarboxylic Acids by Transition-Metal Catalyzed Oxidative Cleavage of Terminal-Unsaturated Fatty Acids. 164, 79-98 (1993). Wexle.r, D., Zink, J. I., and Reber, C. Spectroscopic Manifestations of Potential Surface Coupling Along Normal Coordinates in Transition Metal Complexes. 171,173-204 (1994). Willett, P., see Artymiuk, P. J. 174, 73-104 (1995). 

For the reason of comparison and the development of new domino processes, we have created a classification of these transformations. As an obvious characteristic, we used the mechanism of the different bond-forming steps. In this classification, we differentiate between cationic, anionic, radical, pericyclic, photochemical, transition metal-catalyzed, oxidative or reductive, and enzymatic reactions. For this type... 

During the past few years, increasing numbers of reports have been published on the subject of domino reactions initiated by oxidation or reduction processes. This was in stark contrast to the period before our first comprehensive review of this topic was published in 1993 [1], when the use of this type of transformation was indeed rare. The benefits of employing oxidation or reduction processes in domino sequences are clear, as they offer easy access to reactive functionalities such as nucleophiles (e. g., alcohols and amines) or electrophiles (e. g., aldehydes or ketones), with their ability to participate in further reactions. For that reason, apart from combinations with photochemically induced, transition metal-catalyzed and enzymatically induced processes, all other possible constellations have been embedded in the concept of domino synthesis. 

Warwel, S., Sojka, M., and Rusch, M. Synthesis of Dicarboxylic Acids by Transition-Metal Catalyzed Oxidative Cleavage of Terminal-Unsaturated Fatty Acids. 164, 79-98 (1993). 

The CL reaction of luminol (5-amino-2,3-dihydro-1,4-phthalazinedione) (1) is one of the more commonly used nonenzymatic CL reactions and has been extensively studied [49, 57-59], It is well known that the luminol CL reaction is catalyzed by many kinds of substances, e.g., ozone, halogen-Fe complex, hemin, hemoglobin, persulfate, and oxidized transition metals. The most acceptable scheme is shown in Figure 10. Luminol forms a six-membered ring of peroxide (3) from a diazaquinone intermediate (2) and then, by the decomposition of 3, N2 gas and the Si-excited state of the phthalate dianion are produced, yielding... 

In earlier studies the in vitro transition metal-catalyzed oxidation of proteins and the interaction of proteins with free radicals have been studied. In 1983, Levine [1] showed that the oxidative inactivation of enzymes and the oxidative modification of proteins resulted in the formation of protein carbonyl derivatives. These derivatives easily react with dinitrophenyl-hydrazine (DNPH) to form protein hydrazones, which were used for the detection of protein carbonyl content. Using this method and spin-trapping with PBN, it has been demonstrated [2,3] that protein oxidation and inactivation of glutamine synthetase (a key enzyme in the regulation of amino acid metabolism and the brain L-glutamate and y-aminobutyric acid levels) were sharply enhanced during ischemia- and reperfusion-induced injury in gerbil brain. 

Han, L.-B. and Tanaka, M. Transition metal-catalyzed addition reactions of H-heteroatom and inter-heteroatom bonds to carbon-carbon unsaturated linkages via oxidative additions, Chem. Commun., 395, 1999. 

Trost et al.59 were the first to report enantioselectivity in the transition metal-catalyzed Alder-ene reaction. Several different acids were surveyed for the degree of efficacy in oxidizing the Pd(0) precursor to the active Pd(n) species and for compatibility with the catalyst, substrate, and product. Among acids surveyed were several chiral carboxylic acids products of reactions using these optically active acids were formed with modest enantioselectivity. (A)-binaphthoic acid gave the most promising result, with the cyclized product 83 obtained with 33% ee (Equation (52)). 

Alcohols have always been the major group of hydrogen donors. Indeed, they are the only hydrogen donors that can be used in Meerwein-Ponndorf-Verley (MPV) reductions. 2-Propanol (16) is most commonly used both in MPV reductions and in transition metal-catalyzed transfer hydrogenations. It is generally available and cheap, and its oxidation product, acetone (14), is nontoxic and can usually be removed readily from the reaction mixture by distillation. This may have the additional advantage that the redox equilibrium is shifted even more into the direction of the alcohol. As a result of sigma inductive electronic ef-... 

In this chapter, theoretical studies on various transition metal catalyzed boration reactions have been summarized. The hydroboration of olefins catalyzed by the Wilkinson catalyst was studied most. The oxidative addition of borane to the Rh metal center is commonly believed to be the first step followed by the coordination of olefin. The extensive calculations on the experimentally proposed associative and dissociative reaction pathways do not yield a definitive conclusion on which pathway is preferred. Clearly, the reaction mechanism is a complicated one. It is believed that the properties of the substrate and the nature of ligands in the catalyst together with temperature and solvent affect the reaction pathways significantly. Early transition metal catalyzed hydroboration is believed to involve a G-bond metathesis process because of the difficulty in having an oxidative addition reaction due to less available metal d electrons. 

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