On the way to chiral epoxidations with methyltrioxorhenium(VII) derived catalysts

Methyltrioxorhenium(VII) (MTO) is successfully applied as chiral epoxidation catalysts in the presence of H2O2 as oxidizing agent and excess chiral Lewis base ligands derived from pyrazole. Moderate enantiomeric excesses up to ca. 30% can be reached at low reaction temperatures (−30 °C), the conversions however, being quite low (<25%). The reason for this may be the fluctionality of the N-base ligand. Glycolate complexes of MTO, applied under the same conditions reach somewhat higher enantiomeric excesses (up to ca. 40%), however, again associated with low conversions (<30%). In this case the sensitivity of the catalyst to water induced ligand removal as well as to ligand exchange with other diols is the most likely reason. Nevertheless, the enantiomeric excesses reported here are among the best observed for MTO derived catalytic systems reported to date and more active and selective systems seem feasible.