Abstract

AbstractVenturello’s phosphotungstate complex and titanium(IV) isopropoxide [Ti(O‐i‐Pr)4] were successfully used as catalysts for the epoxidation‐alcoholysis of glycals using hydrogen peroxide [H2O2]. Reaction substrates included a range of variously protected glycals and different alcohols were used as solvents. Ti(O‐i‐Pr)4 was only effective in methanol as solvent, but gave methyl glycosides in high yields and high selectivities. The Venturello complex proved to be a very versatile and efficient catalyst. Apart from epoxidation‐alcoholysis in alcoholic solvents it also showed activity in biphasic conditions to allow for glycosylation of long‐chain alcohols and was very effective in the stereoselective dihydroxylation of benzylated glucal.

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