Abstract
The enantioselective epoxidation of olefin by MnII(R,R-PMCP)(OTf)2, H2O2 and H2SO4 was explored by DFT calculations and experiments. Theoretical results suggest that [MnV(O)(R,R-PMCP)(SO4)]+ species with a triplet ground spin state serves as the active species for the olefin epoxidation. It can be generated by the H2SO4 assisted O-O heterolysis of MnIII(OOH) species. MnIII-persulfate is also involved in this system, but it cannot promote the olefin epoxidation directly, preferring instead to transform into MnV(O). Actually, the asymmetric epoxidation reactions with H2O2/H2SO4 or Oxone provide similar enantioselectivity in the presence of manganese catalyst. These observations further support the transformation of MnIII-persulfate to MnV(O) species.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
