title: Synthesis of α-O- and α-S-glycosphingolipids related to Sphingomonous cell wall antigens using anomerisation.
abstract: Analogues of glycolipids from Spingomonadacaece with O- and S- and SO2-linkages have been prepared using chelation induced anomerisation promoted by TiCl4. Included are examples of the anomerisation of intermediates with O- and S-glycosidic linkages as well as isomerisation of β-thioglycuronic acids (β-glycosyl thiols). The β-O-glucuronide and β-O-galacturonide precursors were efficiently prepared using benzoylated trichloroacetimidates. β-Glycosyl thiols were precursors to β-S-derivatives. Triazole containing mimics of the natural glycolipids were prepared using CuI promoted azide-alkyne cycloaddition reactions in THF. The glycolipid antigens are being evaluated currently for their effects on iNKT cells.
authors.affiliation: School of Chemistry and Chemical Biology, University College Dublin, Dublin 4, Ireland.
authors.forename: Wayne
authors.initials: W
authors.lastname: Pilgrim
authors.forename: Ciaran
authors.initials: C
authors.lastname: O'Reilly
authors.forename: Paul V
authors.initials: PV
authors.lastname: Murphy
mesh_terms: D000942:Antigens, Bacterial / Q000737:chemistry*; D002236:Carbohydrate Conformation; D002384:Catalysis; D002473:Cell Wall / Q000737:chemistry*; D006028:Glycosphingolipids / Q000138:chemical synthesis*; D006031:Glycosylation; D042301:Sphingomonadaceae / Q000737:chemistry; D013237:Stereoisomerism; D014025:Titanium / Q000737:chemistry
chemical_list: D000942:Antigens, Bacterial; D006028:Glycosphingolipids; D014025:Titanium
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