Synthesis of branched D-xylofuranan by selective, ring-opening polymerization of silylated 1,5-anhydro-beta-D-xylofuranose, and its conversion into a blood anticoagulant.
Selective ring-opening polymerization and copolymerization of 1,5-anhydro-D-xylofuranose derivatives were studied. Stereoregular (1----5)-alpha-D-xylofuranan was synthesized from a new monomer, 1,5-anhydro-2,3-di-O-(tert-butyldimethylsilyl)-beta-D-xylofuranose , with phosphorus pentafluoride and antimony pentachloride as catalysts in dichloromethane. Copolymerization of 3 with 1,5-anhydro-2,3-di-O-benzyl-beta-D-xylofuranose, and desilylation of the copolymer with tetrabutylammonium fluoride gave a partially benzylated stereoregular (1----5)-alpha-D-xylofuranan which was glycosylated with 3,4,6-tri-O-acetyl-beta-D-mannose 1,2-(methyl orthoacetate) to give a branched polymer. Deprotection of the benzylated polymer having D-mannosyl branches with sodium in liquid NH3 gave (1----5)-alpha-D-xylofuranans having 2- or 3-O-alpha-D-mannopyranosyl branches. Sulfation of the free D-xylofuranans was achieved with piperidine sulfate. The sulfated D-xylofuranan having branches showed high blood-anticoagulant activity.
Yoshida
T
T
Institute of Industrial Science, University of Tokyo, Japan.
Arai
T
T
Mukai
Y
Y
Uryu
T
T
D000818:Animals; D000925:Anticoagulants / Q000138:chemical synthesis*; D001777:Blood Coagulation / Q000187:drug effects; D002417:Cattle; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D009904:Optical Rotation; D011134:Polysaccharides / Q000138:chemical synthesis* / Q000494:pharmacology; D013329:Structure-Activity Relationship; D013464:Sulfuric Acids / Q000138:chemical synthesis / Q000494:pharmacology; D014994:Xylose / Q000138:chemical synthesis* / Q000494:pharmacology
D000925:Anticoagulants; D007202:Indicators and Reagents; D011134:Polysaccharides; D013464:Sulfuric Acids; D014994:Xylose