title: Catalytic stereoselective glycosidation with glycosyl diphenyl phosphates: rapid construction of 1,2-cis-alpha-glycosidic linkages.
abstract: A commercially available 0.1 M solution of HClO(4) in dioxane has been shown to catalyze the glycosidation of glycosyl diphenyl phosphates. The per-O-benzyl-protected glucosyl and galactosyl donors and the 3,4,6-tri-O-acetyl-2-azido-2-deoxygalactosyl donor each react with a range of acceptor alcohols in the presence of 0.05-0.2 equiv of HClO(4) in dioxane/Et(2)O (1:1) to afford glycosides in good yields with good to excellent alpha selectivities. The synthetic utility of this glycosidation method was demonstrated by a stereoselective synthesis of the alpha-galactosylceramide KRN7000, an activator of natural killer (NK) T cells through CD1d molecules.
authors.affiliation: Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan.
authors.forename: Miyuki
authors.initials: M
authors.lastname: Koshiba
authors.forename: Noritoshi
authors.initials: N
authors.lastname: Suzuki
authors.forename: Ryoichi
authors.initials: R
authors.lastname: Arihara
authors.forename: Toshifumi
authors.initials: T
authors.lastname: Tsuda
authors.forename: Hisanori
authors.initials: H
authors.lastname: Nambu
authors.forename: Seiichi
authors.initials: S
authors.lastname: Nakamura
authors.forename: Shunichi
authors.initials: S
authors.lastname: Hashimoto
mesh_terms: D000438:Alcohols / Q000737:chemistry; D001713:Biphenyl Compounds / Q000737:chemistry*; D002384:Catalysis; D006027:Glycosides / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D010710:Phosphates / Q000737:chemistry*; D012997:Solvents; D013237:Stereoisomerism; D013696:Temperature; D013997:Time Factors
chemical_list: D000438:Alcohols; D001713:Biphenyl Compounds; D006027:Glycosides; D010710:Phosphates; D012997:Solvents; C010574:biphenyl