CALCULATIONS ON THE REACTION OF RUTHENIUM TETRAOXIDE WITH OLEFINS USING DENSITY-FUNCTIONAL THEORY (DFT) - IMPLICATIONS FOR THE POSSIBILITY OF INTERMEDIATES IN THE OSMIUM-CATALYZED ASYMMETRIC DIHYDROXYLATION (AD)

Density functional theory (DFT) calculations were performed on several Ru(VI) and Ru(VIII) complexes to investigate the mechanism of the dih ydroxylation of olefins catalyzed by OsO4 and RuO4. Experimental and c alculated data agree well in the case of known compounds. Some metalla oxetanes have been shown to be energetically accessible, and they are, therefore, feasible as intermediates in the reaction. These calculati ons form a basis for the rationalization of the high enantioselectivit y in the asymmetric dihydroxylation reaction.