Synthesis of Two Tetrasaccharides Related to the O-Antigen from Azospirillum brasilense S17 and Azospirillum lipoferum SR65

Abstract

Synthesis of two isomeric tetrasaccharides, β-D-Glup-(1→2)-α-L-Rhap-(1→3)-α-L- Rhap-(1→2)-α-L-Rhap (I) and β-D-Glup-(1→3)-α-L-Rhap-(1→3)-α-L-Rhap-(1→3)-α-L-Rhap (II), the repeating units from the lipopolysaccharides of the nitrogen-fixing bacterium Azospirillum brasilense S17 and Azospirillum lipoferum SR65, was achieved via assembly of the building blocks 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl trichloroacetimidate (2), p-methoxyphenyl 3,4-di-O-benzoyl-α-L-rhamnopyranoside (3), 3-O-allyloxycarbonyl-2,4-di-O-benzoyl-α-L-rhamnopyranosyl trichloroacetimidate (6), 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl trichloroacetimidate (8), and p-methoxy phenyl 2,4-di-O-benzoyl-α-L-rhamnopyranoside (14). Condensation of 3 with 6 or 8 provided the disaccharides 9 or 11, respectively. Deallyloxycarbonylation of 11 gave the disaccharide aceptor 12, while removal of the p-methoxyphenyl group in 9 followed by trichloroacetimidation of the anomeric hydroxyl group afforded the disaccharide donor 10. Meanwhile, disaccharide donor 16 and acceptor 18 were prepared from 6, 8, and 14 similarly. Finally, condensation of 10 with 12 or 16 with 18, followed by deprotection, gave the target tetrasaccharides I or II, respectively.