Synthesis of a terminal A-B-C disaccharide fragment of flambamycin, curamycin, and avilamycin.
Methyl 2,6-dideoxy-4-O-[2,6-dideoxy-4-O-(3,5-dichloro-4-hydroxy-2-methoxy-6- methylbenzoyl)-beta-D-arabino-hexopyranosyl]-alpha-D-arabino-he xopyranoside (25) corresponds to an A-B-C disaccharide subunit of the title antibiotics. It was synthesized from suitably protected monosaccharide and aromatic precursors. The readily available 4,6-O-benzylidene-1,2-O-(R)-propylidene-alpha-D-glucopyranose was converted in six steps into 2-O-acetyl-4-O-benzoyl-3-O-benzyl-6-deoxy-alpha-D-glucopyranosyl bromide, which was condensed with methyl 3-O-benzyl-2,6-dideoxy-alpha-D-arabino-hexopyranoside in the presence of mercury(II) cyanide. Methyl 4-O-(2-O-acetyl-4-O-benzoyl-3-O-benzyl-6-deoxy-beta- D-glucopyranosyl)-3-O-benzyl-2,6-dideoxy-alpha-D-arabino-hexopyranosi de was converted either into methyl 2,6-dideoxy-4-O-(6-deoxy-beta-D- glucopyranosyl)-alpha-D-arabino-hexopyranoside by removal of the protective groups or into methyl 3-O-benzyl-4-O-(3-O-benzyl-2,6-dideoxy-beta-D-arabino-hexopyranosyl)-2,6 - dideoxy-alpha-D-arabino-hexopyranoside (22) by selective deacetylation, Barton deoxygenation, and Zemplén debenzoylation. Disaccharide 22 was deprotonated with butyllithium and treated with 4-benzyloxy-3,5-dichloro-2-methoxy-6-methylbenzoyl chloride to give the title compound 25 after hydrogenolysis.
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Institut für Organische Chemie, Rheinisch-Westfälischen Technischen Hochschule Aachen, Germany.
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D000900:Anti-Bacterial Agents / Q000737:chemistry*; D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D004187:Disaccharides / Q000138:chemical synthesis* / Q000737:chemistry; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008969:Molecular Sequence Data; D009844:Oligosaccharides / Q000737:chemistry*; D009904:Optical Rotation
D000900:Anti-Bacterial Agents; D004187:Disaccharides; D007202:Indicators and Reagents; D009844:Oligosaccharides; C084691:flambamycin; C006653:avilamycin