Synthesis of four structural elements of xylose-containing carbohydrate chains from N-glycoproteins

János Kerékgyártó, Johannis P. Kamerling, Jan B. Bouwstra, Johannes F G Vliegenthart, A. Lipták

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Abstract

The synthesis of the oligosaccharides β-d-Xylp-(1→2)-β-d-Manp-OMe (12), β-d-Xylp-(1→2)-[α-d-Manp-(1→6)]-β-d-Manp-OMe (17), β-d-Xylp-(1→2)-[α-d-Manp-(1→3)]- β-d-Manp-OMe (21), and β-d-Xylp-(1→2)-[α-d-Manp-(1→3)][α-d-Manp-(1→6)]-β-d-Manp-OMe (25) is described. Methyl 3-O-benzyl-4,6-O-isopropylidene-β-d-mannopyranoside (6) was prepared from the corresponding gluco-epimer (4) by oxidation, followed by stereoselective reduction. Condensation of 6 with 2,3,4-tri-O-acetyl-α-d-xylopyranosyl bromide in the presence of mercuric cyanide gave a 1:9 mixture of methyl 3-O-benzyl-4,6-O-isopropylidene-2-O-(2,3,4-tri-O-acetyl-α- (7a) and -β-d-xylopyranosyl)-β-d-mannopyranoside (7), and then 7 was converted into the acetylated disaccharide-glycoside 11. Regioselective mannosylation, with 2,3,4,6-tetra-O-acetyl-α-d-mannopyranosyl bromide, at position 6 of deisopropylidenated 7 (8), using mercuric bromide as a promoter, afforded the trisaccharide-glycoside derivative 13, which was transformed into the acetylated trisaccharide-glycoside 16. The disaccharide derivative 10, obtained from 8, and the trisaccharide derivative 15, obtained from 13, were glycosylated at position 3 with O-(2,3,4,6-tetra-O-acetyl-α-d-mannopyranosyl)trichloroacetimidate (19), using trimethylsilyl triflate as a promoter, giving rise to acetylated tri- (20) and tetra-saccharide (24) derivatives, respectively. O-Deacetylation of 11, 16, 20, and 24 gave 12, 17, 21, and 25, respectively.

Original languageEnglish
Pages (from-to)51-62
Number of pages12
JournalCarbohydrate Research
Volume186
Issue number1
DOIs
Publication statusPublished - Feb 15 1989

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Trisaccharides
Xylose
Glycosides
Glycoproteins
Disaccharides
Carbohydrates
Mannose
Derivatives
Bromides
Oligosaccharides
Condensation
Oxidation
propylene

ASJC Scopus subject areas

  • Biochemistry
  • Molecular Biology
  • Organic Chemistry

Cite this

Synthesis of four structural elements of xylose-containing carbohydrate chains from N-glycoproteins. / Kerékgyártó, János; Kamerling, Johannis P.; Bouwstra, Jan B.; Vliegenthart, Johannes F G; Lipták, A.

In: Carbohydrate Research, Vol. 186, No. 1, 15.02.1989, p. 51-62.

Research output: Contribution to journalArticle

Kerékgyártó, János ; Kamerling, Johannis P. ; Bouwstra, Jan B. ; Vliegenthart, Johannes F G ; Lipták, A. / Synthesis of four structural elements of xylose-containing carbohydrate chains from N-glycoproteins. In: Carbohydrate Research. 1989 ; Vol. 186, No. 1. pp. 51-62.
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abstract = "The synthesis of the oligosaccharides β-d-Xylp-(1→2)-β-d-Manp-OMe (12), β-d-Xylp-(1→2)-[α-d-Manp-(1→6)]-β-d-Manp-OMe (17), β-d-Xylp-(1→2)-[α-d-Manp-(1→3)]- β-d-Manp-OMe (21), and β-d-Xylp-(1→2)-[α-d-Manp-(1→3)][α-d-Manp-(1→6)]-β-d-Manp-OMe (25) is described. Methyl 3-O-benzyl-4,6-O-isopropylidene-β-d-mannopyranoside (6) was prepared from the corresponding gluco-epimer (4) by oxidation, followed by stereoselective reduction. Condensation of 6 with 2,3,4-tri-O-acetyl-α-d-xylopyranosyl bromide in the presence of mercuric cyanide gave a 1:9 mixture of methyl 3-O-benzyl-4,6-O-isopropylidene-2-O-(2,3,4-tri-O-acetyl-α- (7a) and -β-d-xylopyranosyl)-β-d-mannopyranoside (7), and then 7 was converted into the acetylated disaccharide-glycoside 11. Regioselective mannosylation, with 2,3,4,6-tetra-O-acetyl-α-d-mannopyranosyl bromide, at position 6 of deisopropylidenated 7 (8), using mercuric bromide as a promoter, afforded the trisaccharide-glycoside derivative 13, which was transformed into the acetylated trisaccharide-glycoside 16. The disaccharide derivative 10, obtained from 8, and the trisaccharide derivative 15, obtained from 13, were glycosylated at position 3 with O-(2,3,4,6-tetra-O-acetyl-α-d-mannopyranosyl)trichloroacetimidate (19), using trimethylsilyl triflate as a promoter, giving rise to acetylated tri- (20) and tetra-saccharide (24) derivatives, respectively. O-Deacetylation of 11, 16, 20, and 24 gave 12, 17, 21, and 25, respectively.",
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AU - Kamerling, Johannis P.

AU - Bouwstra, Jan B.

AU - Vliegenthart, Johannes F G

AU - Lipták, A.

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N2 - The synthesis of the oligosaccharides β-d-Xylp-(1→2)-β-d-Manp-OMe (12), β-d-Xylp-(1→2)-[α-d-Manp-(1→6)]-β-d-Manp-OMe (17), β-d-Xylp-(1→2)-[α-d-Manp-(1→3)]- β-d-Manp-OMe (21), and β-d-Xylp-(1→2)-[α-d-Manp-(1→3)][α-d-Manp-(1→6)]-β-d-Manp-OMe (25) is described. Methyl 3-O-benzyl-4,6-O-isopropylidene-β-d-mannopyranoside (6) was prepared from the corresponding gluco-epimer (4) by oxidation, followed by stereoselective reduction. Condensation of 6 with 2,3,4-tri-O-acetyl-α-d-xylopyranosyl bromide in the presence of mercuric cyanide gave a 1:9 mixture of methyl 3-O-benzyl-4,6-O-isopropylidene-2-O-(2,3,4-tri-O-acetyl-α- (7a) and -β-d-xylopyranosyl)-β-d-mannopyranoside (7), and then 7 was converted into the acetylated disaccharide-glycoside 11. Regioselective mannosylation, with 2,3,4,6-tetra-O-acetyl-α-d-mannopyranosyl bromide, at position 6 of deisopropylidenated 7 (8), using mercuric bromide as a promoter, afforded the trisaccharide-glycoside derivative 13, which was transformed into the acetylated trisaccharide-glycoside 16. The disaccharide derivative 10, obtained from 8, and the trisaccharide derivative 15, obtained from 13, were glycosylated at position 3 with O-(2,3,4,6-tetra-O-acetyl-α-d-mannopyranosyl)trichloroacetimidate (19), using trimethylsilyl triflate as a promoter, giving rise to acetylated tri- (20) and tetra-saccharide (24) derivatives, respectively. O-Deacetylation of 11, 16, 20, and 24 gave 12, 17, 21, and 25, respectively.

AB - The synthesis of the oligosaccharides β-d-Xylp-(1→2)-β-d-Manp-OMe (12), β-d-Xylp-(1→2)-[α-d-Manp-(1→6)]-β-d-Manp-OMe (17), β-d-Xylp-(1→2)-[α-d-Manp-(1→3)]- β-d-Manp-OMe (21), and β-d-Xylp-(1→2)-[α-d-Manp-(1→3)][α-d-Manp-(1→6)]-β-d-Manp-OMe (25) is described. Methyl 3-O-benzyl-4,6-O-isopropylidene-β-d-mannopyranoside (6) was prepared from the corresponding gluco-epimer (4) by oxidation, followed by stereoselective reduction. Condensation of 6 with 2,3,4-tri-O-acetyl-α-d-xylopyranosyl bromide in the presence of mercuric cyanide gave a 1:9 mixture of methyl 3-O-benzyl-4,6-O-isopropylidene-2-O-(2,3,4-tri-O-acetyl-α- (7a) and -β-d-xylopyranosyl)-β-d-mannopyranoside (7), and then 7 was converted into the acetylated disaccharide-glycoside 11. Regioselective mannosylation, with 2,3,4,6-tetra-O-acetyl-α-d-mannopyranosyl bromide, at position 6 of deisopropylidenated 7 (8), using mercuric bromide as a promoter, afforded the trisaccharide-glycoside derivative 13, which was transformed into the acetylated trisaccharide-glycoside 16. The disaccharide derivative 10, obtained from 8, and the trisaccharide derivative 15, obtained from 13, were glycosylated at position 3 with O-(2,3,4,6-tetra-O-acetyl-α-d-mannopyranosyl)trichloroacetimidate (19), using trimethylsilyl triflate as a promoter, giving rise to acetylated tri- (20) and tetra-saccharide (24) derivatives, respectively. O-Deacetylation of 11, 16, 20, and 24 gave 12, 17, 21, and 25, respectively.

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