Degradation carbonyl group formation

Thermo-oxidative studies have also been reported on polyisoprenes and on natural rubber. In the latter case, the effect of relative molecular weight on thermo-oxidation as evidenced by carbonyl group formation was investigated. A mechanism for formation of isoprene during thermal degradation of natural rubber has been proposed. It involves a cyclic intermediate. 

Some cleavage takes place even if the phenoHc hydroxyl is blocked as an ether link to another phenylpropane unit and quinonemethide formation is prevented. If the a- or y-carbon hydroxyl is free, alkaH-catalyzed neighboring-group attack can take place with epoxide formation and P-aryloxide elimination. In other reactions, blocked phenoHc units are degraded if an a-carbonyl group is present. 

N-Acetylneuraminic acid aldolase (or sialic acid aldolase, NeuA EC 4.1.3.3) catalyzes the reversible addition of pyruvate (2) to N-acetyl-D-mannosamine (ManNAc (1)) in the degradation of the parent sialic acid (3) (Figure 10.4). The NeuA lyases found in both bacteria and animals are type I enzymes that form a Schiff base/enamine intermediate with pyruvate and promote a si-face attack to the aldehyde carbonyl group with formation of a (4S) configured stereocenter. The enzyme is commercially available and it has a broad pH optimum around 7.5 and useful stability in solution at ambient temperature [36]. 

It should be noted that if the non-phenolic Ca-carbonyl compound contains an aromatic ring without Ca-carbonyl group (i.e., the structure should contain at least two aromatic rings), then the compound will be a substrate for lignin peroxidase and will be degraded according to the mechanisms discussed above. Degradation of this type of compounds can result, for example, in the formation of vanillin and vanillic acid derivatives (see compounds 7a and 8). As has been shown by Eriksson and coworkers... 

In 1973, the group led by Prof. Adinolfi synthetized the antibiotic LL-Z1271a (63) [81] starting from ketolactone 139, obtained, in turn, by degradation of the diterpene marrubiin (9% overall yield). This synthesis basically consists of the formation of the 5-lactone C ring by nucleophilic addition to carbonyl group and subsequent lactonization (Scheme 11).. 

The Reduction Reactions. The object of the next three reactions (steps 4 to 6 in fig. 18.12a) is to reduce the 3-carbonyl group to a methylene group. The carbonyl is first reduced to a hydroxyl by 3-ketoacyl-ACP reductase. Next, the hydroxyl is removed by a dehydration reaction catalyzed by 3-hydroxyacyl-ACP dehydrase with the formation of a trans double bond. This double bond is reduced by NADPH catalyzed by 2,3-trans-enoyl-ACP reductase. Chemically, these reactions are nearly the same as the reverse of three steps in the j6-oxidation pathway except that the hydroxyl group is in the D-configuration for fatty acid synthesis and in the L-configuration for /3 oxidation (compare figs. 18.4a and 18.12a). Also remember that different cofactors, enzymes and cellular compartments are used in the reactions of fatty acid biosynthesis and degradation. 

The volatile components identified from the reaction of cystine and DMHF in aqueous medium are shown in Table I. 2,4-Hexanedione, 3,5-dimethyl-l,2,4-trithiolanes and thiophenes are the major compounds. The mechanistic relationship of the three thiophenones produced has been postulated (23). The major groups of volatile components identified from the reaction in the glycerol medium are 1,3-dioxolanes and thiazoles (Table II). 1,3-Dioxolanes are formed by the reaction of glycerol and the degraded carbonyls by ketal or acetal formations. Comparison of the reaction of cystine and DMHF in water and in glycerol is outlined in Table III. 

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