Asymmetric Aerobic Oxidation of α-Hydroxy Acid Derivatives by <i>C</i><sub>4</sub>-Symmetric, Vanadate-Centered, Tetrakisvanadyl(V) Clusters Derived from <i>N</i>-Salicylidene-α-aminocarboxylates Chien-Tien Chen Sampada Bettigeri Shiue-Shien Weng Vijay D. Pawar Ya-Hui Lin Cheng-Yuan Liu Way-Zen Lee 10.1021/jo070575f.s005 https://acs.figshare.com/articles/journal_contribution/Asymmetric_Aerobic_Oxidation_of_Hydroxy_Acid_Derivatives_by_i_C_i_sub_4_sub_Symmetric_Vanadate_Centered_Tetrakisvanadyl_V_Clusters_Derived_from_i_N_i_Salicylidene_aminocarboxylates/2978464 A series of chiral vanadyl(V) methoxides bearing 3-<i>t</i>-butyl-5-substituted <i>N</i>-salicylene-l-valinate and l-<i>t</i>-leucinate as chiral auxiliaries has been prepared. In all cases except the 3,5-di-<i>t</i>-butyl analogue, they exist as monomers both in solution and in the single crystal state. In the case of the 3,5-di-<i>t</i>-butyl analogue, the architectural nature of the vanadyl(V) complex highly depends on the base used during the complex formation event. A pentanuclear <i>C</i><sub>4</sub>-symmetric complex was formed when potassium salts were employed instead of the corresponding sodium salts. A central vanadate(V) unit serves to grip four identical chiral monomeric vanadyl(V) units together, by which a potassium ion sits on top of the four flanking units through carbonyl coordinations and serves to hold the whole cluster by cooperation with the central vanadate(V) unit. In comparison with the corresponding monomeric vanadyl(V) methoxide complex, the cluster complex was utilized to facilitate the asymmetric aerobic oxidations of various racemic α-hydroxyesters, -amides, and -thioesters with excellent selectivity factors (<i>k</i><sub>rel</sub> 40 to >500). 2007-10-26 00:00:00 di methoxide chiral pentanuclear C 4 Asymmetric Aerobic Oxidation k rel 40 vanadyl potassium cluster monomeric vanadate butyl analogue