Regio- and Stereo-Selective Transformation of Glycosides to Amino-glycosides : Practical Synthesis of Amino-sugars, 4-Amino-4-deoxy-D-galactose, 4-Amino-4-deoxy-L-arabinose, 3-Amino-3-deoxy-D-allose, 3-Amino-3-deoxy-D-glucose, 3-Amino-3-deoxy-D-ribose, 3-Amino-3-deoxy-D-xylose, 2-Amino-2-deoxy-D-mannose, and 5-Amino-5-deoxy-D-glucose (Nojirimycin)

Abstract

One of the hydroxyl groups in glycosides was regio- and stereo-selectively converted to an amino group as follows. A glycoside was regioselectively converted to an oxo-glycoside by bis-tributyltin oxide-bromine oxidation. Oximation of this and reduction of the resulting oxime in a stereoselective manner gave an amino-glycoside in a satisfactory yield.By application of this method, 4-amino-4-deoxy-D-galactose, 4-amino-4-deoxy-L-arabinose, 3-amino-3-deoxy-D-allose, 3-amino-3-deoxy-D-glucose, 3-amino-3-deoxy-D-ribose, 3-amino-3-deoxy-D-xylose, and 2-amino-2-deoxy-D-mannose were synthesized in satisfactory yields from D-xylose or D-glucose as their α- or β-methyl glycosides. The method also provided a practical synthetic route to nojirimycin (5-amino-5-deoxy-D-glucose), a glucosidase-inhibitory antibiotic, from D-glucose.