Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
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.
采用密度泛函理论（DFT）计算研究了苯并四唑（BTM）催化的氮杂环丁酮动力学拆分对映选择性的起源。快速反应对映异构体的过渡态通过酰胺羰基与结合到亲核试剂上的醋酸根阴离子之间的静电相互作用稳定。手性 BTM 催化剂限制了α-碳的构象和亲核进攻的面选择性，以促进这种静电吸引。
