SYNTHESIS OF NEOGLYCOPROTEINS CONTAINING 5-O-PHOSPHORYLATED KDO-MONOSACCHARIDE, 4-O-PHOSPHORYLATED AND 5-O-PHOSPHORYLATED ALPHA-KDO-](2 6)-2-ACETAMIDO-2-DEOXY-BETA-D-GLUCOPYRANOSYL DISACCHARIDE RESIDUES

Radical addition of cysteamine to anomeric allyl glycosides of Kdo 5-p hosphates 1 and 4 afforded good yields of the corresponding 3-(2-amino ethylthio)propyl glycosides. Similar reactions with the alpha-allyl gl ycoside of Kdo 4-phosphate 7 led to substantial formation of the depho sphorylated product 10 through intramolecular hydrolysis of the 4-O-ph osphomonoester by the terminal amino function of the spacer group. Sim ilar side reactions occurred upon deblocking of the 4-O-phosphorylated 6-aminohexyl-alpha-glycoside lactone derivative 18. Allyl glycosides of 4'-O- and 5'-O-phosphorylated Kd--> (2 6)-glucosamine derivatives w ere prepared in good yields via phosphorylation using the amidite proc edure. The 4'-phosphate moiety was introduced following intramolecular protection of the 5'-OH group as a lactone. Subsequent deprotection g ave the allyl glycosides 25 and 33 which were transformed into the cor responding stable spacer derivatives 26 and 34 by coupling with cystea mine. The ligands were activated with thiophosgene and reacted with bo vine serum albumin to give the neoglycoconjugates 3, 6, 27 and 35 to b e used in immunochemical studies of monoclonal antibodies directed aga inst Haemophilus influenzae Re-mutant and related lipopolysaccharides.