Asymmetric aerobic oxidation of alpha-hydroxy acid derivatives by C4-symmetric, vanadate-centered, tetrakisvanadyl(V) clusters derived from N-salicylidene-alpha-aminocarboxylates.
A series of chiral vanadyl(V) methoxides bearing 3-t-butyl-5-substituted N-salicylene-L-valinate and L-t-leucinate as chiral auxiliaries has been prepared. In all cases except the 3,5-di-t-butyl analogue, they exist as monomers both in solution and in the single crystal state. In the case of the 3,5-di-t-butyl analogue, the architectural nature of the vanadyl(V) complex highly depends on the base used during the complex formation event. A pentanuclear C4-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 alpha-hydroxyesters, -amides, and -thioesters with excellent selectivity factors (krel 40 to >500).
Chen
Chien-Tien
CT
Department of Chemistry, National Taiwan Normal University, Taipei, Taiwan, #88, Section 4, Ding-jou Road, Taipei, Taiwan 11650.
Bettigeri
Sampada
S
Weng
Shiue-Shien
SS
Pawar
Vijay D
VD
Lin
Ya-Hui
YH
Liu
Cheng-Yuan
CY
Lee
Way-Zen
WZ
D018360:Crystallography, X-Ray; D006880:Hydroxy Acids / Q000138:chemical synthesis* / Q000737:chemistry; D007930:Leucine / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D014638:Vanadates / Q000737:chemistry*
D006880:Hydroxy Acids; D009942:Organometallic Compounds; D014638:Vanadates; D007930:Leucine