Synthesis of 2,5-anhydro-(beta-d-glucopyranosyluronate)- and (alpha-l-idopyranosyluronate)-d-mannitol hexa-O-sulfonate hepta sodium salt.
Glycosidation of 2,5-anhydro-1,6-di-O-benzoyl-D-mannitol with methyl(2,3,4-tri-O-acetyl-alpha-d-glucopyranosyl-1-O-trichloroacetimidate)uronate in the presence of trimethylsilyl triflate afforded the corresponding 3-O-beta-glycoside, which after deprotection was converted into its hexa-O-sulfate with DMF x SO3 to give after treatment with sodium acetate and subsequent saponification of the methyl ester with sodium hydroxide the hepta sodium salt of 2,5-anhydro-3-O-(beta-d-glucopyranosyl uronate)-D-mannitol hexa-O-sulfate. Glycosidation of the same acceptor with the alpha-thiophenylglycoside of methyl 2,4-di-O-acetyl-3-O-benzyl-L-idopyranosyl uronate in the presence of NIS/TfOH afforded the corresponding 3-O-alpha-glycoside in very low yield, therefore the alpha-thiophenylglycoside of 2-O-acetyl-2,4-O-benzylidene-3-O-benzyl-L-idopyranose was used as donor. The terminal hydroxymethyl group of the obtained disaccharide was subsequently oxidised with NaOCl/TEMPO and the obtained iduronic acid derivative was converted into the hepta sodium salt of 2,5-anhydro-3-O-(-alpha-L-idopyranosyluronate)-D-mannitol hexa-O-sulfonate with DMF x SO3 and subsequent treatment with sodium acetate.
Kuszmann
János
J
IVAX Drug Research Institute, PO Box 82, H-1325 Budapest, Hungary. janos.kuszmann@idri.hu
Medgyes
Gábor
G
Boros
Sándor
S
D002236:Carbohydrate Conformation; D004187:Disaccharides / Q000138:chemical synthesis* / Q000737:chemistry; D020723:Glucuronic Acid / Q000737:chemistry; D006601:Hexoses / Q000737:chemistry; D007067:Iduronic Acid / Q000737:chemistry; D015394:Molecular Structure; D012492:Salts / Q000138:chemical synthesis* / Q000737:chemistry; D019346:Sodium Acetate / Q000737:chemistry; D012972:Sodium Hydroxide / Q000737:chemistry; D013463:Sulfuric Acid Esters / Q000138:chemical synthesis* / Q000737:chemistry; D013865:Thioglycosides / Q000737:chemistry
C494573:2,5-anhydroglucopyranosyluronate-mannitol hexa-O-sulfonate; C494574:2,5-anhydroidopyranosyluronate-mannitol hexa-O-sulfonate; D004187:Disaccharides; D006601:Hexoses; D012492:Salts; D013463:Sulfuric Acid Esters; D013865:Thioglycosides; C010997:idose; D007067:Iduronic Acid; D019346:Sodium Acetate; D012972:Sodium Hydroxide; D020723:Glucuronic Acid