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

Teruaki Mukaiyama; Koki Matsubara; Miyuki Hora

doi:10.1055/s-1994-25695

Synthesis 1994; 1994(12): 1368-1373
DOI: 10.1055/s-1994-25695

paper

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

Teruaki Mukaiyama^* , Koki Matsubara, Miyuki Hora

^*Department of Applied Chemistry, Faculty of Science, Science University of Tokyo, Kagurazaka, Shinjuku-ku, Tokyo 162, Japan

Abstract

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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.

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