Xyluloses

Up to this point all our attention has been directed toward aldoses carbohydrates hav ing an aldehyde function in their open chain form Aldoses are more common than ketoses and their role m biological processes has been more thoroughly studied Nev ertheless a large number of ketoses are known and several of them are pivotal inter mediates m carbohydrate biosynthesis and metabolism Examples of some ketoses include d nbulose l xylulose and d fructose... 

L Xylulose (a 2 ketopentose excreted in excessive amounts in the urine of persons afflicted with the mild genetic disorder pentosuria)... 

Xyhtol (Fig. Ig) is found in the primrose (38) and in minor quantity in mushrooms (39). It can be obtained from glucose in 11.6% overall yield by a sequential fermentation process through D-arabinitol and D-xylulose (28). 

This portion of the pathway begins with an isomerization and an epimeriza-tion, and it leads to the formation of either D-ribose-5-phosphate or D-xylulose-5-phosphate. These intermediates can then be converted into glycolytic intermediates or directed to biosynthetic processes. 

This reaction converts ribulose-5-P to another ketose, namely, xylulose-5-P. This reaction also proceeds by an enediol intermediate, but involves an inversion at C-3 (Figure 23.31). In the reaction, an acidic proton located a- to a carbonyl carbon is removed to generate the enediolate, but the proton is added back to the same carbon from the opposite side. Note the distinction in nomenclature here. Interchange of groups on a single carbon is an epimerization, and interchange of groups between carbons is referred to as an isomerization. 

FIGURE 23.31 The phosphopentose epimerase reaction interconverts ribulose-5-P and xylulose-5-phosphate. The mechanism involves an enediol intermediate and occurs with inversion at C-3. 

One of the steps in the pentose phosphate pathway for glucose catabolism is the reaction of xylulose 5-phosphate with ribose 5-phosphate in the presence of a transketolase to give glyceraldehyde 5-phosphate and sedoheptulose 7-phosphate. 

Thiourea and allylthiourea (20), D-xylulose (22), sodium diethyldithiocarbamate, L-methionine, and -propyl-di- -propylthiol-carbamate (163), 12 6-(substituted) purines (166), and two coumarin derivatives (164) have been found to promote Striga seed germination. None of these materials, however, appear to be constituents of the natural stimulant preparations. 

The trivial names D-erythrulose for D-g/ycero-tetrulose, D-ribulose for D-eryf/iro-pent-2-ulose, and D-xylulose for D-fhreo-pent-2-ulose contain stereochemical redundancy and should not be used for naming derivatives. Sedoheptulose is the accepted trivial name for D-a/rro-hept-2-uIose. 

Ethyl glucopyranuronate GlcpA6Et Xylulose Xylulo (orXul)... 

This thermodynamic driving force is particularly useful tvith multienzyme equilibrium systems such as that used in the gram-scale synthesis of tv ro equivalents ofo-xylulose 5-phosphate (104) from (26) (Figure 10.38) [171,172]. Similarly, the corresponding 1-deoxy-D-xylulose 5-phosphate tvas efficiently produced from pyruvate and (34) by the catalytic action of the thiamine diphosphate-dependent 1-deoxy-D-xylulose 5-phosphate synthase (DXS) (EC 2.2.1.7) from E. coli [173]. 

L-Xylulose Intermediate in uronic acid pathway. 1 I Found in urine in essential pentosuria. 

Ribulose 5-phosphate is the substrate for two enzymes. Ribulose 5-phosphate 3-epimerase alters the configuration about carbon 3, forming another ketopentose, xylulose 5-phosphate. Ribose 5-phosphate ketoisom-erase converts ribulose 5-phosphate to the corresponding aldopentose, ribose 5-phosphate, which is the precursor of the ribose required for nucleotide and nucleic acid synthesis. Transketolase transfers the two-carbon... 

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