2,3-Anhydrosugars in glycoside bond synthesis. Application to 2,6-dideoxypyranosides.
We describe here the first use of 2,3-anhydrosugars as glycosylating agents for the preparation of 2-deoxypyranosides. In particular, the methodology was used to assemble 2,6-dideoxysugar glycosides. Glycosylation of a panel of alcohols with one of two 6-deoxy-2,3-anhydrosugar thioglycosides (8 and 9) in the presence of a Lewis acid afforded 2,6-dideoxy-2-thiotolyl glycoside products in generally excellent yields with an exclusively syn relationship between the aglycon and the C-3 hydroxyl group. Removal of the 2-thiotolyl group can be achieved upon reaction with tri-n-butyltin hydride and AIBN to give the corresponding 2,6-dideoxy pyranosides. Once developed, the method was applied to the synthesis of oligosaccharide moieties in the natural products apoptolidin and olivomycin A.
Hou
Dianjie
D
Alberta Ingenuity Centre for Carbohydrate Science and Department of Chemistry, The University of Alberta, Gunning-Lemieux Chemistry Centre, Edmonton, Alberta T6G 2G2, Canada.
Lowary
Todd L
TL
D001688:Biological Products / Q000138:chemical synthesis; D006027:Glycosides; D006031:Glycosylation; D018942:Macrolides / Q000138:chemical synthesis; D009005:Monosaccharides / Q000138:chemical synthesis*; D009844:Oligosaccharides / Q000138:chemical synthesis; D009848:Olivomycins / Q000138:chemical synthesis
D001688:Biological Products; D006027:Glycosides; D018942:Macrolides; D009005:Monosaccharides; D009844:Oligosaccharides; C025047:olivomycin A; D009848:Olivomycins; C114125:apoptolidin