Regioselective Deacetylation of Fully Acetylated Mono- and Di-Saccharides With Hydrazine Hydrate

Abstract

Selective deacetylation reactions of the peracetylated reducing disaccharides (1), (5), (9), (15), β-D- glucopyranose (17) and 2-acetamido-2-deoxy-β-D-glucopyranose (19), with 1.2 equiv. Of hydrazine hydrate in acetonitrile, gave predominantly the corresponding heptaacetates (2), (6), (10), (16), the tetraacetate (18) and the triacetate (20), with the free hydroxy group at C1. Reaction of (1) with 1.2 equiv. of hydrazine hydrate in N,N- dimethylformamide also afforded the heptaacetate (2), but in lower yield. When reactions of (1), (5) and (9) were performed with 2.5 equiv. of hydrazine hydrate, deacetylation also occurred at other positions to afford the corresponding hexaacetates (3), (7), (11) and (12), with hydroxy groups at C 1,2 or C 1,3, and the pentaacetates (4), (8) and (13), with hydroxy groups at C 1,2,3. Maltose octaacetate (9), in addition, yielded the tetraacetate (14) in which the free hydroxy groups were located at C1,2,2',3. Compound (15) on treatment with 2.5 equiv. of hydrazine hydrate afforded an intractable mixture. The reaction of methyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside (21) with 2.5 equiv. of hydrazine hydrate gave the 3,4,6-triacetate (22), a mixture of the 2,6- and the 3,6-diacetates (23) and (24), respectively, the 4,6-diacetate (25), and the 6-acetate (26).