Origin of enantioselectivity in benzotetramisole-catalyzed dynamic kinetic resolution of azlactones.
Density functional theory (DFT) calculations were performed to investigate the origins of enantioselectivity in benzotetramisole (BTM)-catalyzed dynamic kinetic resolution of azlactones. The transition states of the fast-reacting enantiomer are stabilized by electrostatic interactions between the amide carbonyl group and the acetate anion bound to the nucleophile. The chiral BTM catalyst confines the conformation of the α-carbon and the facial selectivity of the nucleophilic attack to promote such electrostatic attractions.
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
Peng
P
Liu
Xing
X
Yang
Vladimir B
VB
Birman
K N
KN
Houk
D002384:Catalysis; D007700:Kinetics; D007783:Lactones / Q000737:chemistry*; D015394:Molecular Structure; D011789:Quantum Theory; D013237:Stereoisomerism; D013773:Tetramisole / Q000031:analogs & derivatives* / Q000737:chemistry
D007783:Lactones; C515434:benzotetramisole; D013773:Tetramisole