Investigation of the titanium-mediated catalytic enantioselective oxidation of aryl benzyl sulfides containing heterocyclic groups

Abstract

Our enantioselective oxidation protocol, based upon hydroperoxides in the presence of a titanium/(S,S)-hydrobenzoin catalyst, was tested for the first time with aryl benzyl sulfides containing heterocyclic moieties (2-thienyl, 2-pyridyl and benzimidazolyl), two of them being connected with the blockbuster omeprazole drug. Good yields of enantiopure sulfoxides were obtained in most cases. Two exceptions of unsatisfactory enantioselectivity in the oxidation of benzimidazolyl sulfides are reported. However, one of them was solved by crystallization of an enantio-enriched mixture. The present work was supported also by X-ray diffraction analysis of some synthesized sulfoxides and by energetic calculation of the crystal structures. The unexpected result is that the crystal structures of the racemic mixture of the two problematic benzimidazolyl sulfoxides are composed of separate enantiomers (a conglomerate), an interesting result that could be exploited in the future for the separation of the enantiomers of these sulfoxides.