A series of chiral oxovanadium(IV) complexes derived from tridentate N-3,5-substituted and N-3,4-benzo- and N-5,6-benzo-salicylidene-α-amino acids can serve as efficient catalysts for the enantioselective oxidative couplings of various 3-,6-,7-substituted- 2-naphthols under O2 and oxidation of sulfides with H2O2 and Mukaiyama-type aldol additions. The best scenario involves the use of a vanadyl complex arising from 2-hydroxy-1-naphtholaldehyde and valine (or phenylalanine) in CCl4, leading to BINOLs in good yields (75-100%) and with enantioselectivities of up to 68%. Various sulfides can give corresponding sulfoxides by this catalytic reagent also. In case of thioansole, it can be performed with H2O2 (35%), a cheap and safe oxidant, as well as with 5 mol% vanadium catalyst at -20 oC. We are not only reduce the generation of sulfinate, but retain the catalytic reactivity. In addition, these type of vanadium complexes are utilized for Mukayaima additions between benzaldehyde and silyl ketene aectal (SKA) derived from γ-butyrolactone by 10 mol% catalyst at -78 oC in CH2Cl2 to afford aldol products in 45-90% yield with diastereoselectivities of up to 5/95 (syn/anti) and 50%ee (for anti). Remarkably, there were no reported about enantiomeric excess in this case before. On the other hand, four different aromatic aldehydes were also examined. We herein describe our preliminary finding.