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-alpha-amino acids can serve as efficient catalysts for the enantioselective oxidative couplings of various 3-, 6-, and 7-substituted 2-naphthols under O(2). The best scenario involves the use of a vanadyl complex arising from 2-hydroxy-1-naphthaldehyde and valine (or phenylalanine) in CCl(4), leading to BINOLs in good yields (75-100%) and with enantioselectivities of up to 68%.

[reaction--see text] Among four vanadyl species examined, vanadyl triflate was the most efficient catalyst to facilitate nucleophilic acyl substitution of anhydrides with a myriad array of alcohols, amines, and thiols in high yields and high chemoselectivity. By using mixed-anhydride technique, one can achieve oleate and peptide syntheses. In marked contrast to common metal triflates, the amphoteric character of the V=O unit in vanadyl species was proven to be responsible for the catalytic profile in this process.

Condensation of vanadyl sulfate with 2,2'-biphenol in the presence of N-containing ligands provides oxovanadium(IV) complexes which serve as efficient catalysts in Mukaiyama aldol reactions to afford aldol products in 52-100% yields with diastereoselectivities of up to 90/10 (anti/syn)

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