Origin of Enantioselectivity in Benzotetramisole-Catalyzed Dynamic Kinetic Resolution of Azlactones
Origin of Enantioselectivity in Benzotetramisole-Catalyzed Dynamic Kinetic Resolution of Azlactones
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DOI：
10.1021/ol301243f
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发表时间：
2012-07-06
期刊：
影响因子：
5.2
通讯作者：
Houk, K. N.
中科院分区：
文献类型：
--
作者：
Liu, Peng;Yang, Xing;Houk, K. N.
采用密度泛函理论 (DFT) 计算来研究苯并四咪唑 (BTM) 催化的二氢唑酮动态动力学拆分中对映选择性的起源。快速反应的对映体的过渡态通过酰胺羰基和与亲核试剂结合的乙酸根阴离子之间的静电相互作用来稳定。手性BTM催化剂限制了α-碳的构象和亲核攻击的面选择性，以促进这种静电吸引。
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 a-carbon and the facial selectivity of the nucleophilic attack to promote such electrostatic attractions.