Highly Efficient Catalytic Asymmetric Epoxidation of Allylic Alcohols by an Oxovanadium-Substituted Polyoxometalate with a Regenerative TADDOL-Derived Hydroperoxide

The oxovanadium(IV) sandwich-type POM catalyzes the chemo-, regio-, and stereoselective epoxidation of allylic alcohols by chiral hydroperoxides with very high catalytic efficiency (up to 42 000 TON), a potentially valuable oxidation for the development of sustainable processes. By using the sterically demanding, TADDOL-derived hydroperoxide TADOOH as the chiral oxygen source, enantiomeric ratios (er) of up to 95:5 have been achieved.