Synthesis of the 5-aminopentyl glycoside of β-D-Galp-(1->4)-β-D-GlcpNAc-(1->3)-L-Fucp and fragments thereof related to glycopeptides of human Christmas factor and the marine sponge Microciona prolifera

Article abstract of DOI:10.1016/0008-6215(94)84179-9

The marine sponge Microciona prolifera and human coagulation factor IX (Christmas factor)-related mono- to tri-saccharide 5-aminopentyl glycosides β-D-Galp-R (5), β-D-GlcpNAc-R (16), β-D-Galp-(1->4)-β-D-GlcpNAc-R (26), β-D-GlcpNAc-(1->3)-β-L-Fucp-R (39), β-D-GlcpNAc-(1->3)-α-L-Fucp-R (43), β-D-Galp-(1->4)-β-D-GlcpNAc-(1->3)-β-L-Fucp-R (45), and β-D-Galp-(1->4)-β-D-GlcpNAc-(1->3)-α-L-Fucp-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-trichloroethoxycarbonylamino)-α-D-glucopyranosyl trichloroacetimidate (10) and 1,3,4,6-tetra-O-acetyl-2-chloroacetamido-2-deoxy-β-D-glucopyranose (13) were condensed with N-Z-protected 5-aminopentanol (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 β- (32) and α- (37) -L-fucopyranosides, to give the disaccharides 39 and 43, respectively.Starting from lactose, O-(2,3,4,6-tetra-O-benzoyl-β-D-galactopyranosyl)-(1->4)-3,6-di-O-benzoyl-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-α-D-glucopyranosyl 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.Key words: Christmas factor, human; Coagulation factor IX; Human marine sponge Microciona prolifera; Aminopentyl glycoside