1.Origin of enantioselectivity in benzotetramisole-catalyzed dynamic kinetic resolution of azlactones.
Liu P1, Yang X, Birman VB, Houk KN. Org Lett. 2012 Jul 6;14(13):3288-91. doi: 10.1021/ol301243f. Epub 2012 Jun 11.
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.