Synthesis of the 2''-Hydroxy, 4''-Deoxy and 4''-Epi Analogues of beta-D-GalNAc-(1->3)-alpha-D-Gal-(1->4)-beta-D-Gal, the Terminal Trisaccharide of Globotetraose.

Abstract

Radical deoxygenation of methyl 3,6-di-O-benzoyl-2-deoxy-4-O-imidazol-1-yl-thiocarbonyloxy-2-phtha limido-beta-D - glucopyranoside 5 gave methyl 3,6-di-O-benzoyl-2,4-dideoxy-2-phthalimido-beta-D-glucopyranoside 6, which was converted into the corresponding methyl thioglycoside donor 9. Methylsulfenyl trifluoromethane-sulfonate-promoted glycosylation of 2-(trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-(2,4,6-tri-O-benzyl-alpha-D-galactopyranosyl)-bet a-D- galactopyranoside 10, followed by removal of protecting groups gave the 4"-deoxy analogue 12 of the terminal trisaccharide of globotetraose. Silver trifluoromethanesulfonate-promoted glycosylation of the same disaccharide alcohol 10 with 3,4,6-tri-O-acetyl-2-deoxy-2- phthalimido-alpha/beta-D-glucopyranosyl bromide 13 and 2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl bromide 16, followed by deblocking, gave the 2"-hydroxy and 4"-epi analogues 15 and 18, respectively.