Bimetallic titanium complex catalyzed enantioselective oxidation of thioethers using aqueous H2O2 as a terminal oxidant

Abstract

A series of dimeric amino alcohol derived Schiff bases with various chiral amino alcohols and their corresponding bimetallic titanium complex were generated in situ. Thereafter with the in situ generated complexes, the asymmetric oxidation of prochiral aryl alkyl sulfides has been investigated using aqueous H₂O₂ as a terminal oxidant. During the study we found that the use of methanol or tert-butanol as an additive improved the catalytic activity in terms of both conversion and enantioselectivity. Moreover we observed a co-operative effect of the two reactive units of the bimetallic complex, which results in high reactivity as well as enantioselectivity compared to the corresponding monomeric complex. With this improved catalytic system several aryl alkyl sulfides and 1,3-dithianes were oxidised to the corresponding sulfoxides with good to high enantioselectivity (ee 78–99%) and conversion (70–99%). Unlike the monomer, oxidation of substrates like benzyl phenyl sulfide was achieved with high enantioselectivity as well as high yield.