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.