Organic synthesis defined

Abstract For many years after its discovery, olefin metathesis was hardly used as a synthetic tool. This situation changed when well-defined and stable carbene complexes of molybdenum and ruthenium were discovered as efficient precatalysts in the early 1990s. In particular, the high activity and selectivity in ring-closure reactions stimulated further research in this area and led to numerous applications in organic synthesis. Today, olefin metathesis is one of the... 

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. 

A number of synthetic procedures are available (Ai2). (2) For precisely defined stoichiometries, the isobaric, two-bulb method of Herold is preferred H5, H6, H2). (2) To generate compounds suitable for organic synthesis work, graphite and alkali metal may be directly combined, and heated under inert gas (Pl, lA). (5) Electrolysis of fused melts has been reported to be effective iN2). 4) Although alkali metal -amine solutions will react with graphite, solvent molecules co-inter-calate with the alkali metal. Utilization of alkali metal-aromatic radical anion solutions suffers the same problem. 

Photochemical reactions have the principal advantage of clean chemistry , as they use light of defined energy [72, 74], Synthesis of vitamin D and photocleavage of protection groups, for example, are accepted organic synthesis routes. Nevertheless, no widespread use of photochemistry has been made so far as this technique... 

Carbohydrate metabolism in the organism tissues encompasses enzymic processes leading either to the breakdown of carbohydrates (catabolic pathways), or to the synthesis thereof (anabolic pathways). Carbohydrate breakdown leads to energy release or intermediary products that are necessary for other biochemical processes. The carbohydrate synthesis serves for replenishment of polysaccharide reserve or for renewal of structural carbohydrates. The effectiveness of various routes of carbohydrate metabolism in tissues and organs is defined by the availability of appropriate enzymes in them. 

A common striking feature is the simultaneous appearance in all these branches of the same concept of molecular engineering which can be defined as a voluntary and hopefully predictive chemical action, at microscopic level, on the physico-chemical property of interest and has proved to be in many cases a successfull and unifying approach. The same attempt is also existent in the study of inorganic materials but the innumerable possibilities of organic synthesis, and the higher chemical reactivity of organic... 

Initial reports of cross-metathesis reactions using well-defined catalysts were limited to simple isolated examples the metathesis of ethyl or methyl oleate with dec-5-ene catalysed by tungsten alkylidenes [13,14] and the cross-metathesis of unsaturated ethers catalysed by a chromium carbene complex [15]. With the discovery of the well-defined molybdenum and ruthenium alkylidene catalysts 3 and 4,by Schrock [16] and Grubbs [17],respectively, the development of alkene metathesis as a tool for organic synthesis began in earnest. 

Equal or nonuniform distribution of spin density can occur among individual atoms of the molecular carcass. This kind of distribution defines the activity of one or another position in an ion-radical. From the point of view of organic synthesis, properties of ion-radicals such as stability, resistance to active medium components, capacity to disintegrate in the required direction, and... 

Strong bases in dry solvents are usually used in organic synthesis to generate reactive enol anions from ketones. Nevertheless, the kinetic studies discussed here were mostly performed on aqueous solutions. Apart from the relevance of this medium for biochemical reactions and green chemistry, it has the advantage of a well-defined pH-scale permitting quantitative studies of acid and base catalysis. 

Olefin metathesis has proved to be a powerful synthetic tool in organic synthesis.5 The advent of well-defined metal carbene complexes with remarkable functional group tolerance has rendered metathesis as an efficient route to the synthesis of new C-C bonds. Examples of widely used ruthenium metathesis catalysts include [Ru-1],6 [Ru-2]7 and [Ru-3] 8 (Figure 1). 

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