Fructose reaction with

Glucosamine, one of the eight essential monosaccharides (Section 25.7), is biosjmthesized as its 6-phosphate derivative from fructose 6-phosphate by-reaction with ammonia. Propose a mechanism. 

Simple sugars undergo reaction with phenylhydrazine, PhNHNH2, to yield crystalline derivatives called osazones. The reaction is a bit complex, however, as shown by the fact that glucose and fructose yield the same osazone. 

Fructose 6-phosphate is phosphorylated by reaction with ATP to yield fructose 1,6-bisphosphate. 

Step 3 of Figure 29.7 Phosphorylation Fructose 6-phosphate is converted in step 3 to fructose 1,6-bisphosphate (FBP) by a phosphofmctokinase-catalyzed reaction with ATP (recall that the prefix bis- means two). The mechanism is similar to that in step 1, with Mg2+ ion again required as cofactor. Interestingly, the product of step 2 is the tv anomer of fructose 6-phosphate, but it is the (3 anomer that is phos-phorylated in step 3, implying that the two anomers equilibrate rapidly through the open-chain form. The result of step 3 is a molecule ready to be split into the two three-carbon intermediates that will ultimately become two molecules of pyruvate. 

An important metabolic reaction of disaccharides is the reverse of (5). Water, in the presence of H+(aq), reacts with sucrose to give glucose and fructose. This process is called hydrolysis, meaning reaction with water."... 

Figure 20 Post-column detection of mono- and disaccharides with 4-amino-benzoylbenzamide. Column CarboPac PA-1. Gradient 1-10 mm NaOH (0-20 min.), 10-20 mM NaOH (20-35 min). Flow rate 1 ml/min. Detection absorbance at 400 nm after reaction with 4-aminobenzoylhydrazide. (a) Standard mixture of fucose (1), arabinose (2), galactose (3), glucose (4), xylose and N-acetylglucosamine (5 and 6), allose (7), 3-fucosyllactose (8), fructose (9), lactose (10), Man-(3-(l,4)-GlcNac. (b) Normal urine, (c) Urine from a child with (3-mannosidosis. (Reproduced with permission of Academic Press from Peelen, G. O. H., de Jong, J. G. N., and Wever, R. A., Anal. Biochem., 198, 334, 1991.)...

Fischer1-2 decided that the mode of formation, the reactions with hydrazines, aromatic diamines, and oxidizing agents, and the reduction to D-fructose could be explained by attributing to the open-chain form of D-glucosone the a-ketoaldehyde structure L. 

The reaction with ethyl acetoacetate has been extended to glycolaldehyde, and to carbohydrates other than n-glucose, by employing different experimental conditions it is probably applicable to aldoses in general. With d-fructose, yields are lower, but two molar proportions of water are liberated and a crystalline product results. This has a constitution similar to that of II but with the D-omhfno-tetrahydroxybutyl chain at the /3-position on the furan ring. The reaction has been applied successfully to other ketoses and... 

Even more interesting is the observed regioselectivity of 37 its reaction with 2, 3 -cCMP and 2, 3 -cUMP resulted in formation of more than 90% of 2 -phosphate (3 -OH) isomer. The postulated mechanisms for 37 consists of a double Lewis-acid activation, while the metal-bound hydroxide and water act as nucleophilic catalyst and general acid, respectively (see 39). The substrate-ligand interaction probably favors only one of the depicted substrate orientations, which may be responsible for the observed regioselectivity. Complex 38 may operate in a similar way but with single Lewis-acid activation, which would explain the lower bimetallic cooperativity and the lack of regioselectivity. Both proposed mechanisms show similarities to that of the native phospho-monoesterases (37 protein phosphatase 1 and fructose 1,6-diphosphatase, 38 purple acid phosphatase). 

The endo-spiro-OZT could be prepared through a reaction sequence similar to that applied for the exo-epimer, with spiro-aziridine intermediates replacing the key spiro-epoxides (Scheme 18). Cyanohydrin formation from ketones was tried under kinetic or thermodynamic conditions, and only reaction with the d-gluco derived keto sugar offered efficient stereoselectivity, while no selectivity was observed for reaction with the keto sugar obtained from protected D-fructose. The (R) -cyanohydrin was prepared in excellent yield under kinetic conditions (KCN, NaHC03, 0 °C, 10 min) a modified thermodynamic procedure was applied to produce the (S)-epimer in 85% yield (Scheme 18). 

In addition there is other evidence pointing to the fact that the same enzyme is involved in reactions with both D-fructose and L-arabinose. First, the relative rates of reaction with D-fructose and L-arabinose, respectively, remain constant after partial inactivation of the enzyme by heat. Second, the enzyme catalyzing both reactions is produced to a marked extent when sucrose is used as substrate for the growth of the organisms, but not when D-glucose or L-arabinose is used sucrose phos-phorylase is an adaptive enzyme. Third, on fractionation of the enzyme preparation with various concentrations of ammonium sulfate, the relative activities of the fractions are the same for both sugars. These observations indicate not only that the same enzyme is involved in both reactions but also that no additional enzyme is required for the formation of D-glucosyl-L-arabinose. 

There are several examples of one-pot reactions with bifunctional catalysts. Thus, using a bifunctional Ru/HY catalyst, water solutions of corn starch (25 wt.%) have been hydrolyzed on acidic sites of the Y-type zeolite, and glucose formed transiently was hydrogenated on ruthenium to a mixture of sorbitol (96%), mannitol (1%), and xylitol (2%) [68]. Similarly a one-pot process for the hydrolysis and hydrogenation of inulin to sorbitol and mannitol has been achieved with Ru/C catalysts where the carbon support was preoxidized to generate acidic sites [69]. Ribeiro and Schuchardt [70] have succeeded in converting fructose into furan-2,5-dicarboxylic acid with 99% selectivity at 72% conversion in a one-pot reaction... 

Glucose phosphate isomerase 5.3.1.9 Glucose-6-phosphate Fructose-6-phosphate Reaction with resorcinol... 

In order to test these assumptions Heathcock prepared different chiral ketones. Thus, the aldol condensation of the fructose-derived ketone and the acetonide of (/ )-glyceraldehyde gave poor results in the double stereodifferentiation, since an almost equal mixture of the two jyn-aldols 68a and 68b were obtained. However, the reaction with the (5)-aldehyde gave only one syn adduct (69a) (Scheme 9.22) ... 

Dextrose is widely used as an isotonic media in parenteral formulations. Sterilisation using autoclaving has been reported to induce the formation of fructose via an isomerisation reaction, with the resultant formation of 5-hydroxymethyl-furfural [90]. 

Transaldolase, which catalyzes reactions with d-erythrose 4-phosphate and D-fructose 6-phosphate as substrates. As in the case of fructose-1,6-bisphosphate aldolase, this enzyme uses a e-amino side-chain to form a Schiff base intermediate. In this case, however, the triose phosphate moiety is not released but is transferred to the other aldose (in this case, the aldotetrose). 

Intermediate 331 was used in the reaction with ketone-derived sugars 133 (from D-glucose) or 270 (from D-fructose) and with the protected estrone 280 so that, after hydrolysis, diols 337-339"° " were obtained in 25-80% yield. Further cyclization of these diols under Mitsunobu-type reaction conditions (PPh3, DIAD, benzene reflux) gave the mixed heterocyclic sugars 340 and 341"°, and the steroid derivative 342", respectively, in 45-50% yield. 

Hydrolysis is the process by which a compound is broken down by reaction with water, thus it can be thought of as the opposite reaction of dehydration, where water is of course removed. Hydrolysis is a key reaction type in biomass chemistry, for it is central in the depolymerisation of polysaccharides to simpler monosaccharide building blocks, such as fructose, glucose, and xylose. 

Life-threatening adverse reactions with IV sorbitol infusions have been reported in patients with fructose intolerance. 

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