We have developed a series of N-Salicylidene-based L-amino acids as chiral auxiliaries for chiral vanadyl(V) methoxide complex synthesis.In all cases except the 3,5-di-tert-butyl analog,they all exist as monomers both in solution and single crystal state.These configurationally well-defined complexes have been examined for kinetic resolution of 2° alcohols.They serve as efficient and highly enantioselective catalysts for asymmetric aerobic oxidation of-hydroxy acid,1phosphonic acid,2 and ketone derivatives3 at ambient temperature.The asymmetric inductions of the oxidation process are in the range of 50->500 in terms of selectivity factors (krel) in most instances.X-ray crystallographic analysis of an adduct between N-benzyl-mandelamide and the catalyst allows for probing the origin of the nearly exclusive asymmetric control in the oxidation process.In the case of the 3,5-di-tert-butyl analog,a pentanuclear C4-symmetric complex was formed when potassium salts were employed instead of the corresponding sodium salts.The complex works synergistically in the asymmetric aerobic oxidations of various racemic-hydroxy acid derivatives with excellent selectivity factors.3 A directed assembly process to form C4-symmetric,vanadate-centered helical quadruplexes,for the first time,from a given chiral oxidovanadium(V) complex allows for highly efficient K+-,Ag+,Ba2+,Pb2+,and (chiral) ammonium ion-specific transports from aqueous phase into organic solvents,reminiscent of the K+ specific transport exerted by four homochiral glycine residues of the opening site in KcsA membrane protein.