THE SYNTHESIS OF A TRISACCHARIDE AND A TETRASACCHARIDE LIPID INTERMEDIATE. P1-DOLICHYL P2-4)-O-(2-ACETAMIDO-2-DEOXY-β-D-GLUCOPYRANOSYL)-(1->4)-2-ACETAMIDO-2-DEOXY-α-D-GLUCOPYRANOSYL> DIPHOSPHATE AND P1-DOLICHYL P2-3)-O-β...

Article abstract of DOI:10.1016/0008-6215(84)85126-5

Synthetic benzyl O-(2,3,4,6-tetra-O-acetyl-β-D-mannopyranosyl)-(1->4)-O-(2-acetamido-3,6-di-O-acetyl-2-deoxy-β-D-glucopyranosyl)-(1->4)-2-acetamido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranosyide was converted, by catalic hydrogenolysis of the benzyl groups, followed by treatment with acetyl chloride-hydrogen chloride and then "chloride-ion catalysis", into O-(2,3,4,6-tetra-O-acetyl-β-D-mannopyranosyl)-(1->4)-O-(2-acetamido-3,6-di-O-acetyl-2-deoxy-β-D-glucopyranosyl)-(1->4)-2-methyl-(3,6-di-O-acetyl-1,2-dideoxy-α-D-glucopyrano)-<2,1-d>-2-oxazoline.This compound was phosphorylated by treatment with dibenzyl phosphate under strictly anhydrous conditions to give after catalytic hydrogenolysis, a peracetyl trisaccharide phosphate.This was coupled with P¹-dolichyl P²-diphenyl diphosphate to give, after O-deacetylation, P¹-dolichyl P²-4)-O-(2-acetamido-2-deoxy-β-D-glucopyranosyl)-(1->4)-2-acetamido-2-deoxy-α-D-glucopyranosyl> diphosphate, a trisaccharide "lipid intermediate".O-(2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl)-(1->3)-O-(2,4,6-tri-O-acetyl-β-D-mannopyranosyl)-(1->4)-O-(2-acetamido-3,6-di-O-acetyl-2-deoxy-β-D-glucopyranosyl)-(1->4)-(2-acetamido-3,6,-di-O-acetyl-2-deoxy-α-Dglucopyranosyl) phosphate, synthesized from O-α-D-mannopyranosyl-(1->3)-O-β-D-mannopyranosyl-(1->4)-2-acetamido-2-deoxy-D-glucopyranose that had been isolated from mannosidosis urine was coupled with P¹-dolichyl P²-diphenyl diphosphate to give, after O-deacetylation, P¹-dolichyl P²-3)-O-β-D-mannopyranosyl-(1->4)-O-(2-acetamido-2-deoxy-β-D-glucopyranosyl)-(1->4)-2-acetamido-2-deoxy-α-D-glucopyranosyl> diphosphate, a tetrasaccharide "lipid intermediate".