Synthesis of S-linked glucosaminyl-4-thiohex-2-enopyranosides via allylic SN2' substitution of a tosylhexenose.
Treatment of 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio-beta-D-glucopyranose with 1,6-anhydro-3,4-dideoxy-2-O-p-toluenesulfonyl-beta-D-erythro-hex-3-enopyranose gave 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-beta-D-glucopyranosyl-(1-->4)-1,6-anhydro-2,3-dideoxy-4-thio-beta-D-erythro-hex-2-enopyranose in 86% yield. Its 1,6-anhydride bond was cleaved with methanol to give a mixture of methyl glycosides (alpha/beta approximately 5:1), from which the alpha anomer was separated by crystallization and converted into its 6-acetate, 6-methanesulfonate, or deacetylated to obtain the corresponding free methyl thiodisaccharide. The structure of the new compounds was confirmed by 1H and 13C NMR spectra.
Kroutil
J V
JV
Department of Organic Chemistry, Charles University, Cz-128 40 2, Prague, Czech Republic.
Cerný
M
M
Trnka
T V
TV
Budesínský
M
M
D000606:Amino Sugars / Q000138:chemical synthesis*; D004187:Disaccharides / Q000138:chemical synthesis*; D009682:Magnetic Resonance Spectroscopy; D013863:Thioglucosides / Q000138:chemical synthesis*
D000606:Amino Sugars; D004187:Disaccharides; D013863:Thioglucosides