Synthesis of a novel N[bond]O-interglycosidic disaccharide.
The carbohydrate subunits carrying an N-O-interglycosidic bond play a very important role in the biological activity of the enediyne antibiotics. Condensation of O-(alpha- and beta-D-glucopyranosyl)hydroxylamine (5a and 5b) with the hex-3-ulopyranoside (6) furnished methyl 4,6-O-benzylidene-2,3-dideoxy-3-(2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyloxy)imino-alpha- and beta-D-erythro-hexopyranoside (7a and 7b). Stereoselective reduction of the Cz.dbnd6;N bond of 7a and 7b with sodium cyanoborohydride resulted in the formation of the required protected N-O-interglycosidic disaccharides (8a and 8b). Finally, catalytic hydrogenation of 8a afforded methyl 2,3-dideoxy-3-(alpha-D-glucopyranosyloxy)amino-alpha-D-ribo-hexopyranoside (9a). Under similar conditions the beta anomer 8b underwent decomposition.
Hornyák
Miklós
M
Research Group of Antibiotics of the Hungarian Academy of Sciences, and Department of Pharmaceutical Chemistry, University of Debrecen, P.O. Box 70, Debrecen H-4010, Hungary.
Sztaricskai
Ferenc
F
Pelyvás
István F
IF
Batta
Gyula
G
D000617:Aminoglycosides / Q000737:chemistry; D002236:Carbohydrate Conformation; D004187:Disaccharides / Q000138:chemical synthesis / Q000737:chemistry*; D053281:Enediynes; D006027:Glycosides / Q000737:chemistry*; D007536:Isomerism; D009682:Magnetic Resonance Spectroscopy; D009077:Mucins / Q000737:chemistry; D009904:Optical Rotation; D010084:Oxidation-Reduction
D000617:Aminoglycosides; D004187:Disaccharides; D053281:Enediynes; D006027:Glycosides; D009077:Mucins; C055955:calicheamicin gamma(1)I; C047543:esperamicin A1