Glycoside hydrolysis acid catalysis

At the time the mechanism shown in [60] was proposed it was not known whether it was even chemically reasonable. Bimolecular general acid catalysis involving proton transfer in the transition state [equation (45)] had never been observed in the hydrolysis of glycosides or simple acetals. Bronsted and Wynne-Jones (1929) had... 

ACID-CATALYSED HYDROLYSIS OF GLYCOSIDES 3.7.1 Specific Acid Catalysis... 

Intermolecular General Acid Catalysis of Glycoside Hydrolysis... 

Figure 3.17 Molecular mechanisms giving rise to enhanced hydrolysis rates of glycosides with carboxylic acid groups. In the case of salicyl fi-glucoside, frontside nucleophilic attack is stereoelectronically prohibited and distinction between specific acid catalysis of the hydrolysis of the anion and intramolecular general acid catalysis was made on the basis of solvent isotope effects in related systems. ...

Amide participation appears to be about as effective in specific acid-catalysed hydrolysis (of the methyl glycosides) as in spontaneous hydrolysis (of the 2,4-dinitrophenyl glycosides). There is some evidence for simultaneous general acid catalysis and amide participation in the hydrolysis of p-D-GlcNAcp-OoCfiH4COOH. 

Fig. 1 Simultaneous general acid and general base catalysis of glycoside hydrolysis.

Intramolecular general acid catalysis of the hydrolysis of acetals, ketals and glycosides... 

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