Sulfoxidation catalysts generated in situ from titanium(IV) isopropoxide and enantiopure Schiff bases promote the enantioselective oxidation of alkyl aryl sulfides to the corresponding sulfoxides at low catalyst loadings (< 1 mol%), 30% aqueous hydrogen peroxide being the terminal oxidant. Upon screening of several ligands derived from beta-aminoalcohols and salicylaldehydes, a catalyst affording sulfoxides with over 90% chemoselectivity and up to 60% ee was found, and the kinetics of the catalytic reaction was analyzed by H-1 NMR. (c) 2006 Elsevier B.V. All rights reserved.