Catalytic stereoselective glycosidation with glycosyl diphenyl phosphates: rapid construction of 1,2-cis-alpha-glycosidic linkages.
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.
Koshiba
Miyuki
M
Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan.
Suzuki
Noritoshi
N
Arihara
Ryoichi
R
Tsuda
Toshifumi
T
Nambu
Hisanori
H
Nakamura
Seiichi
S
Hashimoto
Shunichi
S
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
D000438:Alcohols; D001713:Biphenyl Compounds; D006027:Glycosides; D010710:Phosphates; D012997:Solvents; C010574:biphenyl