OSMIUM TETRAOXIDE CATALYZED VICINAL HYDROXYLATION OF HIGHER OLEFINS BY USING HEXACYANOFERRATE(III) ION AS A COOXIDANT

The oxidation of olefins with osmium tetraoxide to give cis-diols is a well-established reaction.1 Criegee showed that osmium tetraoxide in a stoichiometric amount could be used for effective cis hydroxylation of the olefins and that this method is more reliable than other diol syntheses,2'3despite its high cost and toxicity. Subsequently, a catalytic amount of osmium tetraoxide has been successfully used in the presence of suitable cooxidants like hydrogen peroxide (Milas' reagent),4-6 metal chlorates,7-9 tert-butyl hydroperoxide,10-12and amine N-oxides (such as N-methylmorpholine TV-oxide, NMO).13 These catalytic hydroxylation reagents, however, have disadvantages due to appreciable overoxidation or inertness toward hindered olefins. We report here a modification of catalytic vicinal hydroxylation using hexacyanoferrate (III) ion as a cheap and convenient cooxidant for osmium(VI). © 1990, American Chemical Society. All rights reserved.