Synthesis of derivatives of 2,3-diamino-2,3-dideoxy-α- d-glucose and 2,3,4-triamino-2,3,4-trideoxy-α- d-glucose

Abstract

This work describes the synthesis of 2,3-diamino-2,3-dideoxy- and 2,3,4-triamino-2,3,4-trideoxy- d-glucose derivatives from α- d-glycosidic 3-deoxy-3-nitro sugars. The reaction of ammonia with methyl 4,6- O-benzylidene-2,3-dideoxy-3-nitro-α- d- erythro-hex-2-enopyranoside ( 1) or with methyl 2- O-acetyl-4,6- O-benzylidene-3-deoxy-3-nitro-α- d-glucoyranoside ( 2) furnished methyl 2-amino-4,6- O-benzylidene-2,3-dideoxy-3-nitro-α- d-glucopyranoside ( 3) in high yield. From 2, a small proportion of an isomeric amine, possibly having the d- manno configuration, arose as a by-product. The N-acetyl derivative 4 of 3 was debenzylidenated to give methyl 2-acetamido-2,3-dideoxy-3-nitro-α- d-glucopyranoside ( 8). Compound 8 was converted by catalytic hydrogenation and subsequent acetylation and hydrolysis into 2,3-diamino-2,3-dideoxy-α- d-glucose dihydrochloride ( 13) and the α- d-glycosidic derivatives 10, 11, and 12. The 4,6-diacetate 9 of 8 reacted with ammonia at room temperature to give methyl 2,4-diacetamido-2,3,4-trideoxy-3-nitro-α- d-glucopyranoside ( 15) in 57% yield. Acetylation of 15 gave its 6-acetate 16, whereas catalytic hydrogenation furnished methyl 2,4-diacetamido-3-amino-2,3,4-trideoxy-α- d-glucopyranoside hydrochloride ( 17), from which the corresponding 2,3,4-triacetamido compound 18 and its 6-acetate 19 were prepared.