Scope and limitations of 2-deoxy- and 2,6-dideoxyglycosyl bromides as donors for the synthesis of β-2-deoxy- and β-2,6-dideoxyglycosides.
It is shown that 2-deoxy- and 2,6-dideoxyglycosyl bromides can be prepared in high yield (72-94%) and engaged in glycosylation reactions with β:α selectivities ≥6:1. Yields of product are 44-90%. Fully armed 2-deoxyglycoside donors are viable, while 2,6-dideoxyglycosides require one electron-withdrawing substituent for high efficiency and β-selectivity. Equatorial C-3 ester protecting groups decrease β-selectivity, and donors bearing an axial C-3 substituent are not suitable. The method is compatible with azide-containing donors and acid-sensitive functional groups.
Department of Chemistry, Yale University , New Haven, Connecticut 06520, United States.
Miho
M
Kaneko
Seth B
SB
Herzon
D001386:Azides / Q000737:chemistry; D020650:Combinatorial Chemistry Techniques; D004583:Electrons; D006027:Glycosides / Q000138:chemical synthesis* / Q000737:chemistry; D006031:Glycosylation; D006842:Hydrocarbons, Brominated / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism
D001386:Azides; D006027:Glycosides; D006842:Hydrocarbons, Brominated