Hydration and Hydrolysis of Radicals

In principal, all steps in these water-elimination reactions are reversible. Because in the reactions discussed above the final products are thermodynamically more stable, the equilibrium lies fully on the right side (i.e., the reverse rates are very slow). However, there are also cases where hydration of a radical is a fast process. For example, reaction (67) occurs at a rate of 2 x 104 s1 (Schuchmann MN and von Sonntag 1988), i.e., a million times faster than the rate of hydration of its non-radical parent, acetaldehyde. 

The hydrolysis of the glycosidic linkage in disaccharides is usually a slow and acid-catalyzed process. It is remarkably speeded up, when at the site of the glycosidic linkage the hydrogen has been replaced by a lone electron [reaction (68)] (for reviews see von Sonntag 1980 von Sonntag and Schuchmann 2001). 

Details have not been investigated. Whether in DNA such a reaction plays also a role in the elimination of the nucleobases from the C(T) radical, is as yet not known. 

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