ON THE STEREOCHEMISTRY OF OSMIUM TETRAOXIDE OXIDATIONS OF ALLYLIC SYSTEMS USED IN THE SYNTHESIS OF HIGHER-CARBON SUGARS

Article abstract of DOI:10.1016/0008-6215(88)84106-5

The stereochemistry of the major osmylation products of carbohydrate-based allylic alcohols can usually be predicted by application of Kishi's empirical rule.In particular, the addition of OsO4 can be formulated as taking place in the more abundant conformation on the surface anti to a pyranose or furanose ring-oxygen atom located at a stereocentre adjacent to the olefinic linkage.Exceptions to Kishi's empirical rule for osmylation are sometimes encountered with conjugated carbonyl compounds.