Hemiacetals oligosaccharides

Carb-37.1. Oligosaccharides without a free hemiacetal group... 

Haworth representation, cyclic monosaccharides, 61-63 Hemiacetal groups disaccharides with, 149-150 without, 148-149 nomenclature, 122-123 oligosaccharides with, 153-154 without, 151-153... 

Silicon presents an attractive option among eledrophilic activating and dehydrating agents of hemiacetals because of the wide commercial availability of eledrophilic silicon sources. The two main classes of silicon electrophiles used, namely silyl halides and silyl sulfonates, have been demonstrated to promote a variety of glycosylations including some examples of oligosaccharide synthesis. 

This procedure has been demonstrated to provide moderate yields and anomeric selectivity in oligosaccharide synthesis. For instance, the disaccharide 110 was obtained in 50% yield as a 1 2 a p ratio. The reaction side products were mainly the self-condensed donor (10-25%) and unreacted hemiacetal (5-10% or higher). Alternatively, the a-linked glycosides were favored with diethyl ether solvent. In this way, trisaccharide 111 was prepared from the disaccharide hemiacetal donor in 49% yield, favoring the a-anomer by 4 1. 

The oligosaccharides commonly encountered in nature belong to disaccharides. The physiologically important disaccharides are maltose, lactose, trehalose and sucrose. Disaccharides consist of two monosaccharides joined covalently by an O-glycosidic bond. The hydroxyl group formed as a result of hemiacetal formation is highly reactive when compared to other hydroxyl groups. This... 

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