Synthesis of 2-acetamido-2-deoxy-6-O-beta-D-galactopyranosyl-D-galactopyranose and o-nitrophenyl 2-acetamido-2-deoxy-6-O-beta-D-galactopyranosyl -alpha-D-galactopyranoside.
Acetalation of o-nitrophenyl 2-acetamido-2-deoxy-alpha-D-galactopyranoside with p-methoxybenzaldehyde-zinc chloride complex afforded the 4,6-O-(p-methoxybenzylidene) derivative (1). Acetylation of 1 with pyridine-acetic anhydride gave the crystalline monoacetate (2), the acetal group of which was cleaved by brief treatment with hot, 80% aqueous acetic acid to furnish the diol (3). The 1H-n.m.r. spectra of both 2 and 3 supported their overall structures. Glycosylation of 3 with 2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl bromide (5) in 1:1 nitromethane-benzene, in the presence of mercuric cyanide, afforded the disaccharide derivative (6). O-Deacetylation of 6 in methanolic sodium methoxide gave the title disaccharide (8). A similar glycosylation of benzyl 2-acetamido-3-O-acetyl-2-deoxy-alpha-D-galactopyranoside with bromide 5, followed by O-deacetylation of the resulting intermediate, produced disaccharide 9. The structures of 8 and 9 were confirmed by 13C-n.m.r. spectroscopy. Hydrogenolysis of the benzyl aglycon of 9 gave the free disaccharide 2-acetamido-2-deoxy-6-O-beta-D-galactopyranosyl-D-galactopyranose (13). The 13C-n.m.r. spectrum of 13 is recorded, and discussed in conjunction with those of the beta-(1----3)- and the beta-(1----4)-linked isomers.
D004187:Disaccharides / Q000138:chemical synthesis*; D009682:Magnetic Resonance Spectroscopy
D004187:Disaccharides; C043179:2-nitrophenyl-2-acetamido-2-deoxy-6-O-beta galactopyranosyl-alpha galactopyranoside; C043178:2-acetamido-2-deoxy-6-O-beta galactopyranosylgalactopyranose