INOR 387

Asymmetric oxidations can provide a convenient and potentially environmentally benign synthetic pathway towards a number of important chiral auxiliaries including chiral sulfoxides.  The peroxo-oxovanadium(V)  complex of hydroxyethyl iminodiacetate^2- (Hheida^2-) was previously shown to be a functional model for vanadium dependent haloperoxidases (VHPO), mimicking both the halide and sulfide oxidation abilities of the enzymes.  This complex shows a significant rate of sulfide oxidation using the terminal oxidant hydrogen peroxide.  To further develop the modeling chemistry of VHPO's, we have synthesized sterically hindered complexes maintaining the electronic structure of Hheida^2-_, and explored their abilities to stereoselectively oxidize thioethers.  The stereoselectivity and rates of oxidation were examined, in addition to the effects of organic peroxides on stereoselectivity and complex stability.