3-O-Sulfo glucuronyl neolactohexanosyl ceramide derivatives (heptasaccharides) have been synthesized. Condensation of 2-(trimethylsilyl)ethyl 2,4,6-tri-O-benzyl-β-D-galactopyranoside (2) with 4-O-acetyl-3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl trichloroacetimidate (1) gave the desired β-glycoside3, which was converted into 2-(trimethylsilyl)ethylO-(2-acetamido-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranosyl)-(1→3)-2,4,6-tri-O-benzyl-β-D-galactopyranoside (4)viaremoval of theO-acetyl andN-phthaloyl groups, followed byN-acetylation. Glycosylation of4withO-(methyl 4-O-acetyl-2-O-benzoyl-3-O-levulinoyl-β-D-glucopyranosyluronate)-(1→3)-2,4,6-tri-O-benzoyl-α-D-galactopyranosyl trichloroacetimidate (5) using trimethylsilyl trifluoromethanesulfonate gave the target tetrasaccharide6, which was transformedviaremoval of the benzyl group,O-benzoylation, removal of the 2-(trimethylsilyl)ethyl group and imidate formation into the tetrasaccharide donor9. Glycosylation of 2-(trimethylsilyl)ethylO-(2-acetamido-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranosyl)-(1→3)-O-(2,4,6-tri-O-benzyl-β-D-galactopyranosyl)-(1→4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside (10) with the imidate donor9using trimethylsilyl trifluoromethanesulfonate gave the desired heptasaccharide11, which was transformed into the heptasaccharide imidate donor14. Glycosylation of (2S, 3R, 4E)-2-azido-3-O-benzoyl-4-octadecene-1,3-diol (15) with14gave β-glycoside16, which was transformed into the four target compounds,viareduction of the azido group, coupling with octadecanoic acid or tetracosanoic acid, selective removal of the levulinoyl group,O-sulfation, hydrolysis of the methyl ester group andO-deacylation.