Importance of Electrostatic Effects in the Stereoselectivity of NHC-Catalyzed Kinetic Resolutions
Importance of Electrostatic Effects in the Stereoselectivity of NHC-Catalyzed Kinetic Resolutions
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DOI：
10.1021/jacs.7b01796
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发表时间：
2017-09-13
影响因子：
15
通讯作者：
Wheeler, Steven E.
中科院分区：
文献类型：
--
作者：
Maji, Rajat;Wheeler, Steven E.
用现代密度泛函理论方法研究了三个N-杂环卡宾（NHC）催化的动力学拆分（KR）和一个动态动力学拆分（DKR）反应，以确定催化活性和选择性的来源以及助催化剂在这些反应中的作用.结果表明，静电相互作用作为选择性的共同驱动程序。此外，在最近描述的BINOL衍生物的KR的情况下，对整个催化循环的计算检查揭示了苯甲酸副产物改变了限制转换步骤的周转，从而避免了对添加的助催化剂的需要。总之，这些数据为NHC催化的动力学拆分的活性和选择性提供了关键见解，并强调了静电相互作用作为选择性驱动因素的重要性。
Three N-heterocyclic carbene (NHC) catalyzed kinetic resolutions (KR) and one dynamic kinetic resolution (DKR) were examined using modern density functional theory methods to identify the origin of catalytic activity and selectivity and the role of cocatalysts in these reactions. The results reveal electrostatic interactions as the common driver of selectivity. Furthermore, in the case of a recently described KR of BINOL-derivatives, a computational examination of the full catalytic cycle reveals that a benzoic acid byproduct changes the turnover limiting transition step, obviating the need for an added cocatalyst. Together, these data provide key insights into the activity and selectivity of NHC-catalyzed kinetic resolutions, and underscore the importance of electrostatic interactions as a driver of selectivity.