Synthesis of a selectively protected trisaccharide building block that is part of xylose-containing carbohydrate chains from N-glycoproteins

János Kerékgyártó, Jos G M van der Ven, Johannis P. Kamerling, A. Lipták, Johannes F G Vliegenthart

Research output: Contribution to journalArticle

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Abstract

The synthesis is reported of ethyl 4-O-[3-O-allyl-4,6-O-isopropylidene-2-O-(2,3,4-tri-O-acetyl-β-d- xylopyranosyl)-β-d-mannopyranosyl]-3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-d-glucopyranoside (16), a key intermediate in the synthesis of xylose-containing carbohydrate chains from N-glycoproteins. Condensation of ethyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-d-glucopyranoside (5) with 2,4,6-tri-O-acetyl-3-O-allyl-α-d-glucopyranosyl bromide, using silver triflate as a promoter, gave the β-linked disaccharide derivative 8 (84%). O-Deacetylation of 8 and then isopropylidenation afforded 10, which was converted via oxidation-reduction into ethyl 4-O-allyl-4,6-O-isopropylidene-β-d-mannopyranosyl)-3, 6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-d-glucopyranoside (12). Silver triflate-promoted condensation of 12 with 2,3,4-tri-O-acetyl-α-d-xylopyranosyl bromide gave 16 (71%). The Xylp unit in 16 and in de-isopropylidenated 16 (17) existed in the 1C4(d) conformation, but that in O-deacetylated 17 (18) existed in the 4C1(d) conformation.

Original languageEnglish
Pages (from-to)135-145
Number of pages11
JournalCarbohydrate Research
Volume238
Issue numberC
DOIs
Publication statusPublished - Jan 15 1993

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Trisaccharides
Xylose
Bromides
Conformations
Condensation
Glycoproteins
Carbohydrates
Disaccharides
Oxidation-Reduction
Derivatives
trifluoromethanesulfonic acid
propylene

ASJC Scopus subject areas

  • Biochemistry
  • Molecular Biology
  • Organic Chemistry

Cite this

Synthesis of a selectively protected trisaccharide building block that is part of xylose-containing carbohydrate chains from N-glycoproteins. / Kerékgyártó, János; van der Ven, Jos G M; Kamerling, Johannis P.; Lipták, A.; Vliegenthart, Johannes F G.

In: Carbohydrate Research, Vol. 238, No. C, 15.01.1993, p. 135-145.

Research output: Contribution to journalArticle

Kerékgyártó, János ; van der Ven, Jos G M ; Kamerling, Johannis P. ; Lipták, A. ; Vliegenthart, Johannes F G. / Synthesis of a selectively protected trisaccharide building block that is part of xylose-containing carbohydrate chains from N-glycoproteins. In: Carbohydrate Research. 1993 ; Vol. 238, No. C. pp. 135-145.
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abstract = "The synthesis is reported of ethyl 4-O-[3-O-allyl-4,6-O-isopropylidene-2-O-(2,3,4-tri-O-acetyl-β-d- xylopyranosyl)-β-d-mannopyranosyl]-3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-d-glucopyranoside (16), a key intermediate in the synthesis of xylose-containing carbohydrate chains from N-glycoproteins. Condensation of ethyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-d-glucopyranoside (5) with 2,4,6-tri-O-acetyl-3-O-allyl-α-d-glucopyranosyl bromide, using silver triflate as a promoter, gave the β-linked disaccharide derivative 8 (84{\%}). O-Deacetylation of 8 and then isopropylidenation afforded 10, which was converted via oxidation-reduction into ethyl 4-O-allyl-4,6-O-isopropylidene-β-d-mannopyranosyl)-3, 6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-d-glucopyranoside (12). Silver triflate-promoted condensation of 12 with 2,3,4-tri-O-acetyl-α-d-xylopyranosyl bromide gave 16 (71{\%}). The Xylp unit in 16 and in de-isopropylidenated 16 (17) existed in the 1C4(d) conformation, but that in O-deacetylated 17 (18) existed in the 4C1(d) conformation.",
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T1 - Synthesis of a selectively protected trisaccharide building block that is part of xylose-containing carbohydrate chains from N-glycoproteins

AU - Kerékgyártó, János

AU - van der Ven, Jos G M

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AU - Lipták, A.

AU - Vliegenthart, Johannes F G

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N2 - The synthesis is reported of ethyl 4-O-[3-O-allyl-4,6-O-isopropylidene-2-O-(2,3,4-tri-O-acetyl-β-d- xylopyranosyl)-β-d-mannopyranosyl]-3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-d-glucopyranoside (16), a key intermediate in the synthesis of xylose-containing carbohydrate chains from N-glycoproteins. Condensation of ethyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-d-glucopyranoside (5) with 2,4,6-tri-O-acetyl-3-O-allyl-α-d-glucopyranosyl bromide, using silver triflate as a promoter, gave the β-linked disaccharide derivative 8 (84%). O-Deacetylation of 8 and then isopropylidenation afforded 10, which was converted via oxidation-reduction into ethyl 4-O-allyl-4,6-O-isopropylidene-β-d-mannopyranosyl)-3, 6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-d-glucopyranoside (12). Silver triflate-promoted condensation of 12 with 2,3,4-tri-O-acetyl-α-d-xylopyranosyl bromide gave 16 (71%). The Xylp unit in 16 and in de-isopropylidenated 16 (17) existed in the 1C4(d) conformation, but that in O-deacetylated 17 (18) existed in the 4C1(d) conformation.

AB - The synthesis is reported of ethyl 4-O-[3-O-allyl-4,6-O-isopropylidene-2-O-(2,3,4-tri-O-acetyl-β-d- xylopyranosyl)-β-d-mannopyranosyl]-3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-d-glucopyranoside (16), a key intermediate in the synthesis of xylose-containing carbohydrate chains from N-glycoproteins. Condensation of ethyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-d-glucopyranoside (5) with 2,4,6-tri-O-acetyl-3-O-allyl-α-d-glucopyranosyl bromide, using silver triflate as a promoter, gave the β-linked disaccharide derivative 8 (84%). O-Deacetylation of 8 and then isopropylidenation afforded 10, which was converted via oxidation-reduction into ethyl 4-O-allyl-4,6-O-isopropylidene-β-d-mannopyranosyl)-3, 6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-d-glucopyranoside (12). Silver triflate-promoted condensation of 12 with 2,3,4-tri-O-acetyl-α-d-xylopyranosyl bromide gave 16 (71%). The Xylp unit in 16 and in de-isopropylidenated 16 (17) existed in the 1C4(d) conformation, but that in O-deacetylated 17 (18) existed in the 4C1(d) conformation.

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