Synthesis of cerebroside, lactosyl ceramide, and ganglioside GM3 analogs containing β-thioglycosidically linked ceramide

Article abstract of DOI:10.1016/S0008-6215(00)90529-9

Coupling of the sodium salt of 2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranose, -β-D-galactopyranose, O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-(1→4)-2,3,6-tri-O- acetyl-1-thio-β-D-glucopyranose, or O-(methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto -2-nonulopyranosylonate)-(2→3)-O-(2,3-di-O-acetyl-6-O-benzoyl-β-D- galactopyranosyl)-(1→4)-3-O-acetyl-2,6-di-O-benzoyl-1-thio-β-D- glucopyranose, which were prepared from the corresponding 1-S-acetates, 1, 3, 6, and 9, with (2S,3R,4E)-2-azido-3-O-benzoyl-1-O-(p-tolylsulfonyl)-4-octadecene- 1,3-diol (12) derived by tosylation of 11, gave the corresponding β-thioglycosides 13, 17, 21, and 25, respectively in good yield. The β-thioglycosides obtained were converted, via selective reduction of the azide group, condensation with octadecanoic acid, and removal of the protecting groups, into the title compounds. Coupling of the sodium salt of 2,3,4,6-tetra-O- acetyl-1-thio-β-D-glucopyranose, -β-D-galactopyranose, O-(2,3,4,6-tetra- O-acetyl-β-D-galactopyranosyl)-(1→4)-2,3, 6-tri-O-acetyl-1-thio- β-D-glucopyranose, or O-(methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3, 5-dideoxy-D-glycero-α- D-galacto-2-nonulopyranosyl-onate)-(2→3) -O-(2,3-di-O-acetyl -6-O-bezoyl-β-D-galactopyranosyl) -(1→4) -3-O-acetyl-2,6-di-O- benzoyl-1-thio-β-D-glucopyranose, which were prepared from the corresponding 1-S-acetates, 1, 3, 6, and 9, with ( 2S,3R,4E)-2-azido-3 -O-benzoyl-1-O-(p-tolylsulfonyl) -4-octadecene-1,3 -diol (12) derived by tosylation of 11, gave the corresponding β-thioglycosides 13, 17, 21, and 25, respectively in good yield. The β-thioglycosides obtained were converted, via selective reduction of the azide group, condensation with octadecanoic acid, and removal of the protecting groups, into the title compounds.