A NOVEL SYNTHESIS FOR AMINODIDEOXY SUGARS: 3-AMINO-2,3-DIDEOXY-D-ARABINO-HEXOSE

Abstract

The 4,6-O-benzylidene derivative II of methyl 3-nitro-3-deoxy-β-D-glucopyranoside (I) was prepared. Its 2-O-acetate (III) was converted by a Schmidt–Rutz reaction into methyl 4,6-O-benzylidene-2,3-dideoxy-3-nitro-β-D-erythro-hexos-2-enide (IV). Selective hydrogenation of the olefinic double bond in IV afforded methyl 4,6-O-benzylidene-2,3-dideoxy-3-nitro-β-D-, arabino-hexopyranoside (V). The debenzylidenated derivative of V (VI) was reduced to methyl 3-amino-2,3-dideoxy-β-D-arabino-hexopyranoside hydrochloride (VII), from which the free reducing sugar (VIII), the N-acetyl glycoside (IX), the N-acetyl glycoside 4,6-di-O-acetate (X), and the N-acetyl glycoside 4,6-di-O-mesylate (XI) were obtained. The solvolysis of XI proceeded with neighboring group participation to give a product of either aziridine (XII) or pyrrolidine (XIII) structure.