Chemical synthesis of the pyruvic acetal-containing trisaccharide unit of the species-specific glycopeptidolipid from Mycobacterium avium serovariant 8

Istv́n Bajza, János Kerékgyárto, János Hajkó, László Szilágyi, András Lipták

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Abstract

The functionalized, pyruvic acetal-containing haptenic trisaccharide, p-trifluoroacetamidophenyl 6-deoxy-2-O-3-O-[4,6-O-(S)-(1-methoxycarbonylethylidene)-3-O-methyl-β-d-glucopyranosyl]-α-l-rhamnopyranosyl-α-l-talopyranoside (19), a component of the glycolipid from Mycobacterium avium serovar 8 was synthesized. For the preparation of the terminal pyruvic acetal-containing unit, benzyl 2-O-benzyl-3-O-methyl-β-d-glucopyranoside (6) was condensed with methyl 2,2-di(ethylthio)propionate (1) in the presence of SO2Cl2CF3SO3H catalyst to yield benzyl 2-O-benzyl-4,6-O-(S)-(1-methoxycarbonylethylidene)-3-O-methyl-β-d-glucopyranoside (7S), which was then converted into the suitably substituted glycosyl donor 2-O-acetyl-4,6-O-(S)-(1-methoxycarbonylethylidene)-3-O-methyl-α-d-glucopyranosyl trichloroacetimidate (11). The disaccharide glycosyl acceptor p-nitrophenyl endo-3,4-O-benzylidene-6-deoxy-2-O-(2,4-di-O-benzyl-α-l-rhamnopyranosyl)-α-l-talopyranoside (15) was glycosylated with 11 in the presence of trimethyl trifluoromethanesulfonate to furnish the protected trisaccharide p-nitrophenyl 2-O-3-O-[2-O-acetyl-4,6-O-(S)(1-methoxycarbonylethylidene)-3-O-methyl-β-d-glucopyranosyl]-2,4-di-O-benzyl-α-l-rhamnopyranosyl-endo-3,4-O-benzylidene-6-deoxy-α-l-talopyranoside (16). After deprotection, this gave the spacer-armed unprotected haptenic trisaccharide 19.

Original languageEnglish
Pages (from-to)111-120
Number of pages10
JournalCarbohydrate Research
Volume253
Issue numberC
DOIs
Publication statusPublished - Feb 3 1994

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Trisaccharides
Mycobacterium avium
Acetals
Disaccharides
Glycolipids
Propionates
Catalysts

ASJC Scopus subject areas

  • Biochemistry
  • Molecular Biology
  • Organic Chemistry

Cite this

Chemical synthesis of the pyruvic acetal-containing trisaccharide unit of the species-specific glycopeptidolipid from Mycobacterium avium serovariant 8. / Bajza, Istv́n; Kerékgyárto, János; Hajkó, János; Szilágyi, László; Lipták, András.

In: Carbohydrate Research, Vol. 253, No. C, 03.02.1994, p. 111-120.

Research output: Contribution to journalArticle

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title = "Chemical synthesis of the pyruvic acetal-containing trisaccharide unit of the species-specific glycopeptidolipid from Mycobacterium avium serovariant 8",
abstract = "The functionalized, pyruvic acetal-containing haptenic trisaccharide, p-trifluoroacetamidophenyl 6-deoxy-2-O-3-O-[4,6-O-(S)-(1-methoxycarbonylethylidene)-3-O-methyl-β-d-glucopyranosyl]-α-l-rhamnopyranosyl-α-l-talopyranoside (19), a component of the glycolipid from Mycobacterium avium serovar 8 was synthesized. For the preparation of the terminal pyruvic acetal-containing unit, benzyl 2-O-benzyl-3-O-methyl-β-d-glucopyranoside (6) was condensed with methyl 2,2-di(ethylthio)propionate (1) in the presence of SO2Cl2CF3SO3H catalyst to yield benzyl 2-O-benzyl-4,6-O-(S)-(1-methoxycarbonylethylidene)-3-O-methyl-β-d-glucopyranoside (7S), which was then converted into the suitably substituted glycosyl donor 2-O-acetyl-4,6-O-(S)-(1-methoxycarbonylethylidene)-3-O-methyl-α-d-glucopyranosyl trichloroacetimidate (11). The disaccharide glycosyl acceptor p-nitrophenyl endo-3,4-O-benzylidene-6-deoxy-2-O-(2,4-di-O-benzyl-α-l-rhamnopyranosyl)-α-l-talopyranoside (15) was glycosylated with 11 in the presence of trimethyl trifluoromethanesulfonate to furnish the protected trisaccharide p-nitrophenyl 2-O-3-O-[2-O-acetyl-4,6-O-(S)(1-methoxycarbonylethylidene)-3-O-methyl-β-d-glucopyranosyl]-2,4-di-O-benzyl-α-l-rhamnopyranosyl-endo-3,4-O-benzylidene-6-deoxy-α-l-talopyranoside (16). After deprotection, this gave the spacer-armed unprotected haptenic trisaccharide 19.",
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AU - Bajza, Istv́n

AU - Kerékgyárto, János

AU - Hajkó, János

AU - Szilágyi, László

AU - Lipták, András

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N2 - The functionalized, pyruvic acetal-containing haptenic trisaccharide, p-trifluoroacetamidophenyl 6-deoxy-2-O-3-O-[4,6-O-(S)-(1-methoxycarbonylethylidene)-3-O-methyl-β-d-glucopyranosyl]-α-l-rhamnopyranosyl-α-l-talopyranoside (19), a component of the glycolipid from Mycobacterium avium serovar 8 was synthesized. For the preparation of the terminal pyruvic acetal-containing unit, benzyl 2-O-benzyl-3-O-methyl-β-d-glucopyranoside (6) was condensed with methyl 2,2-di(ethylthio)propionate (1) in the presence of SO2Cl2CF3SO3H catalyst to yield benzyl 2-O-benzyl-4,6-O-(S)-(1-methoxycarbonylethylidene)-3-O-methyl-β-d-glucopyranoside (7S), which was then converted into the suitably substituted glycosyl donor 2-O-acetyl-4,6-O-(S)-(1-methoxycarbonylethylidene)-3-O-methyl-α-d-glucopyranosyl trichloroacetimidate (11). The disaccharide glycosyl acceptor p-nitrophenyl endo-3,4-O-benzylidene-6-deoxy-2-O-(2,4-di-O-benzyl-α-l-rhamnopyranosyl)-α-l-talopyranoside (15) was glycosylated with 11 in the presence of trimethyl trifluoromethanesulfonate to furnish the protected trisaccharide p-nitrophenyl 2-O-3-O-[2-O-acetyl-4,6-O-(S)(1-methoxycarbonylethylidene)-3-O-methyl-β-d-glucopyranosyl]-2,4-di-O-benzyl-α-l-rhamnopyranosyl-endo-3,4-O-benzylidene-6-deoxy-α-l-talopyranoside (16). After deprotection, this gave the spacer-armed unprotected haptenic trisaccharide 19.

AB - The functionalized, pyruvic acetal-containing haptenic trisaccharide, p-trifluoroacetamidophenyl 6-deoxy-2-O-3-O-[4,6-O-(S)-(1-methoxycarbonylethylidene)-3-O-methyl-β-d-glucopyranosyl]-α-l-rhamnopyranosyl-α-l-talopyranoside (19), a component of the glycolipid from Mycobacterium avium serovar 8 was synthesized. For the preparation of the terminal pyruvic acetal-containing unit, benzyl 2-O-benzyl-3-O-methyl-β-d-glucopyranoside (6) was condensed with methyl 2,2-di(ethylthio)propionate (1) in the presence of SO2Cl2CF3SO3H catalyst to yield benzyl 2-O-benzyl-4,6-O-(S)-(1-methoxycarbonylethylidene)-3-O-methyl-β-d-glucopyranoside (7S), which was then converted into the suitably substituted glycosyl donor 2-O-acetyl-4,6-O-(S)-(1-methoxycarbonylethylidene)-3-O-methyl-α-d-glucopyranosyl trichloroacetimidate (11). The disaccharide glycosyl acceptor p-nitrophenyl endo-3,4-O-benzylidene-6-deoxy-2-O-(2,4-di-O-benzyl-α-l-rhamnopyranosyl)-α-l-talopyranoside (15) was glycosylated with 11 in the presence of trimethyl trifluoromethanesulfonate to furnish the protected trisaccharide p-nitrophenyl 2-O-3-O-[2-O-acetyl-4,6-O-(S)(1-methoxycarbonylethylidene)-3-O-methyl-β-d-glucopyranosyl]-2,4-di-O-benzyl-α-l-rhamnopyranosyl-endo-3,4-O-benzylidene-6-deoxy-α-l-talopyranoside (16). After deprotection, this gave the spacer-armed unprotected haptenic trisaccharide 19.

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