An Efficient Glycosylation Reaction of 1-Hydroxy Sugars with Various Nucleophiles Using A Catalytic Amount of Activator and Hexamethyldisiloxane

Abstract

In the presence of hexamethyldisiloxane and anhydrous calcium sulfate, a catalytic amount of activator such as tin(II) trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate , lanthanum trifluoromethanesulfonate or tin(II) chloride smoothly promotes the glycosylation reactions between 1-hydroxy sugars and free alcohols, electron-rich aromatic compounds or silylated nucleophiles to produce various O -, C - or N - glycosides stereoselectively in high yields. In the case of oxygen or nitrogen nucleophiles, β-ribosides are formed, except that α-ribosides are obtained predominantly in the presence of lithium perchlorate. In the case of carbon nucleophiles such as electron-rich aromatic compounds or silyl enol ethers derived from carbonyl compounds, perfect β-selectivity is shown either in the the presence or absence of lithium perchlorate. Further, pyranosyl substrates such as glucose or galactose afford the corresponding α-anomers, except with electron-rich aromatic compounds.