MTO and OsO4: An Efficient Catalytic Couple for Mild H2O2‐Based Asymmetric Dihydroxylation of Olefins

A novel and robust system for osmium-catalyzed asymmetric dihydroxylation of olefins by aqueous H2O2 with methyltrioxorhenium (MTO) as electron transfer mediator (ETM) has been developed. The MTO is catalyzing the H2O2 oxidation of the chiral ligand to its mono-N-oxide, which in turn reoxidizes OsVI to OsVIII. Thus the (DHQD)2PHAL plays a dual role serving as the chiral inductor as well as the tertiary amine generating the N-oxide required for the recycling of osmium. The present catalytic system gives vicinal diols in good isolated yields and high enantiomeric excess (up to 99 % ee).