Synthesis of some oligosaccharides containing the O-alpha-L-fucopyranosyl-(1----2)-D-galactopyranosyl unit.
A practical approach for the synthesis of oligosaccharides containing the O-alpha-L-fucopyranosyl-(1----2)-D-galactopyranosyl unit has been developed by utilizing the readily accessible 3,4,6-tri-O-acetyl-2-O-(2,3,4-tri-O-acetyl-alpha-L- fucopyranosyl)-alpha-D-galactopyranosyl bromide (1). Thus, condensation of bromide 1 with 8-(methoxycarbonyl)octanol in benzene, in the presence of mercuric cyanide, afforded, after column-chromatographic separation, the anomers (3 and 4) of 8-(methoxycarbonyl)octyl 3,4,6-tri-O-acetyl-2-O-(2,3,4-tri-O-acetyl-alpha-L-fucopyranosyl)-D- galactopyranoside in the ratio of 13:4. On the basis of their specific rotations, compounds 3 and 4 were tentatively assigned the alpha and beta configuration, respectively. Similarly, bromide 1 was allowed to react with some other, appropriately protected sugars having a free alcohol group, to afford the corresponding alpha and beta anomers of a galactopyranosyl residue having an alpha-L-fucopyranosyl substituent at O-2. Column-chromatographic separation of the anomeric mixtures, followed by systematic removal of the protecting groups, then provided the final oligosaccharides desired. In this manner, the synthesis of the following oligosaccharides has been accomplished: alpha-L-Fuc-(1----2)-alpha-D-Gal-1----O(CH2)8CO2Me (5), alpha-L-Fuc-(1----2)-beta-D-Gal-1----O(CH2)8CO2Me (6), alpha-L-Fuc-(1----2)-alpha-D-Gal-(1----3)-beta-D-GlcNAc-1----OC6H4NO2 -p (11), alpha-L-Fuc-(1----2)-beta-D-Gal-(1----3)-beta-D-GlcNAc-1----OC6H4NO2+ ++-p (13), alpha-L-Fuc-(1----2)-alpha-D-Gal-(1----3)-alpha-D-GalNAc-1----OC6H4NO 2-o, and alpha-L-Fuc-(1----2)-beta-D-Gal-(1----3)-alpha-D-GalNAc-1----OC6H4NO2 -o (18).(ABSTRACT TRUNCATED AT 250 WORDS)
D000017:ABO Blood-Group System; D006801:Humans; D007983:Lewis Blood Group Antigens; D009682:Magnetic Resonance Spectroscopy; D009844:Oligosaccharides / Q000138:chemical synthesis*
D000017:ABO Blood-Group System; D007983:Lewis Blood Group Antigens; D009844:Oligosaccharides