Homochiral trialkanolamines are a new class of chiral ligand for enant
ioselective catalysis. Mononuclear titanium complexes bearing such lig
ands promote the asymmetric sulfoxidation of alkyl aryl sulfides. In c
ontrast, a dimeric zirconium species is the active catalyst in the des
ymmetrization of meso epoxides with azides. Mechanistic insight into t
he latter reaction has led to a new reaction, the enantioselective des
ymmetrization of meso epoxides using halides as the nucleophilic partn
er.