Synthese von oligosaccharid-determinanten des T-antigens mit amid-spacer zur darstellung synthetischer antigene

doi:10.1016/S0040-4039(01)90328-4

Tetrahedron Letters

Volume 22, Issue 15, 1981, Pages 1387-1390

https://doi.org/10.1016/S0040-4039(01)90328-4 Get rights and content

Abstract

The β (1 → 3) -linked disaccharide $1$ $5$ was synthesized from $D$ -galactose and a $D$ -galactosamine unit with a watersoluble amide spacer. This represents the hapten of T-antigen and, when coupled to a protein, is suitable for use as an artificial antigen. Other O-β- $D$ -galactosylated derivatives of galactosamine were synthesized.

Literatur (8)

P. Vaith et al.
Z. Immun.-Forsch.
(1978)
G.F. Springer et al.
Clin. Immunol. and Immunopathol.
(1977)
H. Paulsen et al.
Carbohydr. Res.
(1978)
G.F. Springer et al.
Prog. Allergy
(1979)

There are more references available in the full text version of this article.

Cited by (25)

Synthesis of the Sda determinant and two analogous tetrasaccharides
1997, Carbohydrate Research
To contribute to the possibility of studying in greater detail the biological significance of Sd^a-containing glycans as occur in Tamm-Horsfall glycoprotein, the following three spacerlinked tetrasaccharides have been synthesized: the Sd^a determinant $α- Neu p5 Ac -(2 → 3)-[β- d -Gal p NAc -(1 → 4)]-β- d -Gal p-(1 → 4)-β- d -Glc p NAc -(1 → O) (CH_{2})_{5} NH_{2}$ (1), the Gal-analogue $α- Neu p5 Ac -(2 → 3)- [β- d -Gal p-(1 → 4)]-β- d -Gal p-(1 → 4)-β- d -Glc p NAc -(1 → O) (CH_{2})_{5} NH_{2}$ (2), and the GlcNAc-analogue $α- Neu p5 Ac -(2 → 3)-[β- d -Glc p NAc -(1 → 4)]-β- d -Gal p-(1 → 4)-β- d -Glc p NAc -(1 → O) (CH_{2})_{5} NH_{2}$ (3). The general trisaccharide acceptor 5-azidopentyl $(methyl 5-acetamido-4,7,8,9-tetra -O- acetyl-3,5-dideoxy- d -glycero-α- d -galacto- non-2-ulopyranosylonate)-(2 → 3)-(2,6- di -O- benzyl -β- d -galactopyranosyl)-(1 → 4)-3,6- di -O- benzyl-2-deoxy-2-phthalimido -β- d -glucopyranoside$ was prepared, using methyl $(phenyl 5-acetamido-4,7,8,9-tetra -O- acetyl-3,5-dideoxy-2-thio- d -glycero- d -galacto- non-2-ulopyranosid)-onate$ as the sialyl donor. For the syntheses of 1, 2, and 3 the glycosyl donors $3,4,6- tri -O- acetyl-2-deoxy-2-phthalimido -α- d -galactopyranosyl$ bromide, $2,3,4,6- tetra -O- acetyl -α- d -galactopyranosyl$ bromide, and $3,4,6- tri -O- acetyl-2-deoxy-2-phthalimido -β- d -glucopyranosyl$ trichloroacetimidate, respectively, proved to be the most suitable.
Direct access to neoglycoproteins and glycopolymers from single precursors. Synthesis of T-antigen and N-acetyl-lactosamine-β-D-(1→6)-α-D-GalNAc conjugates
1992, Bioorganic and Medicinal Chemistry Letters
A facile enzymatic synthesis of galβ1,3glucal: a key intermediate for the synthesis of Lea and sialyl Lea
1992, Tetrahedron Letters
Study on the carbohydrate specificity of antibodies formed in rabbits to synthetic glycoproteins with the carbohydrate structure of asialo-glycophorin A
1985, Molecular Immunology
Antibodies formed in rabbits to synthetic glycoproteins with the disaccharide structure β-d-Gal-(1–3)-d-GalNAc, the carbohydrate moiety of desialylated glycophorin A, were investigated for their carbohydrate specificity by hemagglutination techniques and radioimmunoassay. The synthetic disaccharide was coupled to human serum albumin as carrier protein using different spacer groups and different configurations of the disaccharide spacer linkage. Radioimmunological inhibition experiments using a number of different derivatives of the carbohydrate group as inhibitors revealed a significant specificity of the antibodies for the oligosaccharide structure. However, the nature of the conjugation of the disaccharide to the carrier protein was found to be important for defining the specificity of the antibodies. Furthermore the arrangement of the hapten groups in the synthetic antigen had an important influence on the antigen-antibody reaction. No cross-reactions were observed between asialo-glycophorin A and the different synthetic antigens. Synthetic antigens provide a valuable tool for generating carbohydrate-specific antibodies. However, if the synthetic hapten molecule is small compared to the combining site of antibodies, the specificity of the immunological reaction is significantly influenced by the synthetic spacer arm or even the carrier protein.
A practical synthesis of 2-acetamido-2-deoxy-3,4-di-O-β-d-galactopyranosyl-d-galactopyranose
1983, Carbohydrate Research
Two different sugar derivatives having free hydroxyl groups have been employed for synthesis of the title trisaccharide. In one attempt, benzyl 2-acetamido-6-O-benzyl-2-deoxy-α-d-galactopyranoside (8) was treated with an excess of 2,3,4,6-tetra-O-acetyl-α-d-galactopyranosyl bromide (11), to give a mixture of products which, on fractionation, afforded benzyl 2-acetamido-6-O-benzyl-3,4-di-O-(2,3,4,6-tetra-O-acetyl-β-d-galactopyranosyl)- α-d-galactopyranoside (15) in 21% yield. However, in another, preferable approach, benzyl 2-acetamido-6-O-benzyl-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-β-d- galactopyranosyl)-α-d-galactopyranoside (13) was treated with 11, to produce 15 in 69% yield. Both 8 and 13 were conveniently prepared via reductive ring-opening of the respective 4,6-benzylidene acetals. O-Deacetylation of 15, followed by hydrogenolysis, provided the title trisaccharide. The structure of the final product, and of various other intermediates, was established by ¹H- and ¹³C-n.m.r. spectroscopy.
Synthese der T-antigenen trisaccharide O-β-d-galactopyranosyl-(1→3)-O-(2-acetamido-2-desoxy-α-d-galactopyranosyl)-(1→6)-d-galactopyranose und O-β-d-galactopyranosyl-(1→3)-O-(2-acetamido-2-desoxy-α-d-galactopyranosyl)-(1→6)-d-glucopyranose und deren anknüpfung an proteine
1983, Carbohydrate Research
The synthesis of the trisaccharides O-β-d-galactopyranosyl-(1→3)-O-(2-acetamido-2-deoxy-α-d-galactopyranosyl)-(1→6)-d-galactopyranose (15) and O-β-d-galactopyranosyl-(1→3)-O-(2-acetamido-2-deoxy-α-d-galactopyranosyl)-(1→6)-d-glucopyranose (27) is described and the synthesis of α-d-glycosides by reaction of 3,4,6-tri-O-acetyl-2-azido-2-deoxy-β-d-galactopyranosyl chloride with highly reactive hydroxyl groups is discussed. The trisaccharide 27 was coupled with serum albumin by formation of an imine intermediate and reduced to an amine, to yield a synthetic T-antigen. A similar coupling of 15 was unsuccessful.

View all citing articles on Scopus

^☆: XXVIII. Mitteil. der Reihe 'Bausteine von Oligosacchariden' XXVII. Mitteil.: $H. Paulsen$ und $R. Jansen$ , Carbohydr. Res. im Druck

View full text

Article preview

Tetrahedron Letters

Abstract

Literatur (8)

Z. Immun.-Forsch.

Clin. Immunol. and Immunopathol.

Carbohydr. Res.

Prog. Allergy

Cited by (25)

Synthesis of the Sd<sup>a</sup> determinant and two analogous tetrasaccharides

Direct access to neoglycoproteins and glycopolymers from single precursors. Synthesis of T-antigen and N-acetyl-lactosamine-β-D-(1→6)-α-D-GalNAc conjugates

A facile enzymatic synthesis of galβ1,3glucal: a key intermediate for the synthesis of Le<sup>a</sup> and sialyl Le<sup>a</sup>

Study on the carbohydrate specificity of antibodies formed in rabbits to synthetic glycoproteins with the carbohydrate structure of asialo-glycophorin A

A practical synthesis of 2-acetamido-2-deoxy-3,4-di-O-β-d-galactopyranosyl-d-galactopyranose

Synthese der T-antigenen trisaccharide O-β-d-galactopyranosyl-(1→3)-O-(2-acetamido-2-desoxy-α-d-galactopyranosyl)-(1→6)-d-galactopyranose und O-β-d-galactopyranosyl-(1→3)-O-(2-acetamido-2-desoxy-α-d-galactopyranosyl)-(1→6)-d-glucopyranose und deren anknüpfung an proteine

Synthese von oligosaccharid-determinanten des T-antigens mit amid-spacer zur darstellung synthetischer antigene☆

Abstract

Z. Immun.-Forsch.

Clin. Immunol. and Immunopathol.

Carbohydr. Res.

Prog. Allergy