Synthesis of O-α-L-Fucopyranosyl-(1→2)-O-β-D-galactopyranosyl-(1→4)-2-acetamido-2-deoxy-D-glucopyranose. The H-Blood Group Specific Trisaccharide

Abstract Different reaction conditions were investigated for the preparation of benzyl 2-acetamido-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranoside (5). Compound 5 on reaction with 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl bromide afforded the 4-O-substituted 2-acetamido-2-deoxy-β-D-glucopyranosyl derivative which, on O-deacetylation, gave benzyl 2-acetamido-3,6-di-O-benzyl-2-deoxy-4-O-β-D-galactopyranosyl-β-D-glucopyranoside (8). The trimethylsilyl (Me3Si) derivative of 8, on treatment with pyridineacetic anhydride-acetic acid for 2 days, gave the disaccharide derivative having an O-acetyl group selectively introduced at the primary position and Me3Si groups at the secondary positions. The latter groups were readily cleaved by treatment with aqueous acetic acid in methanol to afford benzyl 2-acetamido-4-O-(6-O-acetyl-β-D-galactopyranosyl)-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranoside, which on isopropylidenation gave the desired, key intermediate benzyl 2-acetamido-4-O-(6-O-acetyl-3,4-O-isopropylidene-β-D-gal...

[1]  P. Rosevear,et al.  Synthesis and solution conformation of the type 2 blood group oligosaccharide alpha LFuc(1 leads to 2) beta DGal(1 leads to 4) beta DGlcNAc. , 1982, Biochemistry.

[2]  H. Paulsen.  Advances in Selective Chemical Syntheses of Complex Oligosaccharides , 1982 .

[3]  R. Dicioccio,et al.  Substrate specificity and other properties of alpha-L-fucosidase from human serum. , 1982, The Journal of biological chemistry.

[4]  D. I. Rawson,et al.  Assignment of ring size in isopropylidene acetals by carbon-13 n.m.r. spectroscopy , 1982 .

[5]  J. Barlow,et al.  The selective acetylation of primary alcohols in the presence of secondary alcohols in carbohydrates , 1982 .

[6]  J. Barlow,et al.  The chemical synthesis of O-α-l-fucopyranosyl-(1→2)-O-β-d-galactopyranosyl-(1→3)-O-[α-l-fucopyranosyl-(1→4)]-2- acetamido-2-deoxy-d-glucopyranose, the lewis b blood-group antigenic determinant , 1981 .

[7]  H. Hultberg,et al.  A novel, reductive ring-opening of carbohydrate benzylidene acetals, with unusual regioselectivity , 1981 .

[8]  A. Veyrières.  Blood-group li-active oligosaccharides. Synthesis of a tetrasaccharide, a β-(1 → 3) dimer of N-acetyl-lactosamine , 1981 .

[9]  L. Goodman,et al.  Catalytic deacylation of sugars with strong base ion-exchange resins; an alternative to the Zemplén procedure , 1981 .

[10]  J. Jacquinet,et al.  Synthesis of blood-group substances. Part 11. Synthesis of the trisaccharide O-α-D-galactopyranosyl-(1 → 3)-O-β-D-galactopyranosyl-(1 → 4)-2-acetamido-2-deoxy-D-glucopyranose , 1981 .

[11]  H. Flowers,et al.  Chemistry and biochemistry of D- and L-fucose. , 1981, Advances in carbohydrate chemistry and biochemistry.

[12]  J. Petit,et al.  A convenient etherification of the primary hydroxyl group of glucopyranosides , 1980 .

[13]  D. Horton,et al.  Conversion of 2-acetamido-2-deoxy-d-glucose into 2-acetamido-2,6-dideoxy-d-galactose (N-acetyl-d-fucosamine) and its benzyl-3-O-benzyl glycosides , 1978 .

[14]  M. Matsui,et al.  Regioselective enhancement of the nucleophilicity of hydroxyl groups through trialkylstannylation: a route to partial alkylation of polyhydroxy compounds , 1978 .

[15]  J. Lehmann,et al.  Selective 6-O-acetylation of amylose , 1978 .

[16]  S. Oscarson,et al.  Monobenzylation of diols using phase-tramfer catalysis , 1976 .

[17]  J. Jacquinet,et al.  Synthese des substances de groupe sanguin—IV : Synthese du 2-acetamido-2-desoxy-4-O-[2-O-(α-l-fucopyranosyl)-β-d-galactopyranosyl]-d-glucopyranose, porteur de la specificite H☆☆☆ , 1976 .

[18]  R. Lemieux,et al.  Halide ion catalyzed glycosidation reactions. Syntheses of .alpha.-linked disaccharides , 1975 .

[19]  J. Lehmann,et al.  Notiz über eine verbesserte Methode zur spezifischen Freisetzung oder Acylierung primärer Hydroxylgruppen ausgehend von pertrimethylsilylierten Polyolen , 1974 .

[20]  H. G. Fletcher,et al.  The behavior of some aldoses with 2,2-dimethoxypropane-N,N-dimethylformamide-p-toluenesulfonic acid. I. At room temperature (25 degrees). , 1973, Carbohydrate research.

[21]  R. Jeanloz,et al.  The synthesis of 2-acetamido-2-deoxy-4-O-β-d-mannopyranosyl-d-glucose , 1971 .

[22]  W. Morgan,et al.  Isolation of Serologically Active Fucose-Containing Oligosaccharides from Human Blood-Group H Substance , 1964, Nature.