Synthesis of the 5-aminopentyl glycoside of beta-D-Gal p-(1-->4)-beta-D-Glc p NAc-(1-->3)-L-Fuc p and fragments thereof related to glycopeptides of human Christmas factor and the marine sponge Microciona prolifera.
The marine sponge Microciona prolifera and human coagulation factor IX (Christmas factor)-related mono- to tri-saccharide 5-aminopentyl glycosides beta-D-Gal p-R (5), beta-D-Glc pNAc-R (16), beta-D-Gal p-(1-->4)-beta-D-Glc p NAc-R (26), beta-D-Glc p NAc-(1-->3)-beta-L-Fuc p-R (39), beta-D-Glc pNAc-(1-->3)-alpha-L-Fuc p-R (43), beta-D-Gal p-(1-->4)-beta-D- Glc pNAc-(1-->3)-beta-L-Fuc p-R (45), and beta-D-Gal p-(1-->4)-beta-D-Glc p NAc-(1-->3)-alpha-L-Fuc p-R (47), where R is a 5-aminopentyloxy spacer moiety, which allowed the construction of glycoconjugates, were prepared. Thus, 3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2- trichloroethoxycarbonyl-amino)-alpha-D-glucopyranosyl trichloroacetimidate (10) and 1,3,4,6-tetra-O-acetyl-2-chloro-acetamido-2- deoxy-beta-D-glucopyranose (13) were condensed with N-Z-protected 5-amino-pentanol (2) followed by conversion of the coupling products into the corresponding N-acetylglucosamine derivatives, to give compound 16 after deblocking. Similarly, the donors 10 and 13 were coupled to position 3 of suitably protected aminopentyl beta- (32) and alpha- (37) -L-fucopyranosides, to give the disaccharides 39 and 43, respectively. Starting from lactose, O-(2,3,4,6-tetra-O-benzoyl-beta-D-galactopyranosyl)-(1-->4)-3,6-di-O- benzoyl-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-alpha-D-glu copyranosyl trichloroacetimidate (23) was prepared and used as an efficient disaccharide donor for the construction of ligand 26 from 2 and of the trisaccharide ligands 45 and 47 from fucosides 32 and 37, respectively.
Ziegler
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Institut für Organische Chemie und Isotopenforschung, Universität Stuttgart, Germany.
D000818:Animals; D002240:Carbohydrate Sequence; D005164:Factor IX / Q000737:chemistry*; D006020:Glycopeptides / Q000737:chemistry*; D006801:Humans; D008969:Molecular Sequence Data; D015394:Molecular Structure; D011161:Porifera / Q000737:chemistry*; D014312:Trisaccharides / Q000138:chemical synthesis*
D006020:Glycopeptides; D014312:Trisaccharides; C090602:5-aminopentyl O-galactopyranosyl-1-4-O-(2-acetamido-2-deoxyglucopyranosyl)-1-3-fucopyranoside; D005164:Factor IX