Glucose 6-phosphate tautomerism

Glucose 6-phosphate is isomerized to fructose 6-phosphate by ring opening followed by a keto-enol tautomerization. 

Following hydrolysis, keto-enol tautomerization of the carbonyl group from C2 to Cl gives glucose 6-phosphate. The isomerization is the reverse of step 2 in glycolysis. 

Both D-[l- C]xylose and D-[5- C]arabinose were exposed to a concentrated phosphate buffer solution (pH 6.7). 1-Hydroxy-2-propanone (ace-tol) was distilled from the heated solution. Radioassay indicated that similar labeling [3- C] occurred in the acetol from both pentoses, with loss of the configurational difference thus, a 3-ketopentose or its enediol was suggested as an intermediate. Further work with 3-0- and 6-0-methyl-D-glucose and with 1-0-methyl-D-fructose indicated that /3-elimination from a 3-ketose or, in the case of a hexose, from a 3-ketose or a 4-ketose, or both, tautomerization of the resulting a-diketone to a /3-diketone, and hydrolytic cleavage are essential steps in the formation of acetol. 

Glucose 6-phosphate is then isomerized to fructose 6-phosphate. This conversion of an aldose sugar to a ketose sugar is easy to rationalize in terms of keto-enol tautomerism (see Box 10.1). 

This is achieved by two keto-enol tautomerism reactions and a common enol (see Box 10.1). Mechanistically, it is identical to the isomerization of glucose 6-phosphate to fructose 6-phosphate seen earlier in the sequence, so we can move on to the next step of the pathway. 

Step 2 is an isomerization, in which the pyranose ring of glucose 6-phosphate opens, tautomerism causes isomerization to fructose 6-phosphate, and a furanose ring is formed. 

Phosphorylation and isomerization. Glucose, produced by the digestion of dietary carbohydrate., is first phosphorylated at the hydroxyl group on C6 by reaction with ATP in a process catalyzed by the enzyme hexokinase. The glucose 6-phosphate that results is isomerized by glucose 6-phosphate isomerase to fructose 6-phosphate. As the open-chain structures in Figure 29.4 show, this isomerization reaction takes place by keto-enol tautomerism (Section 22.1), since both glucose and fructose share a common enol ... 

One pathway for the metabolism of D-glucose 6-phosphate is its enzyme-catalyzed conversion to D-fructose 6-phosphate. Show that this transformation can be accomplished as two enzyme-catalyzed keto-enol tautomerisms. 

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