Stacking and Electrostatic Interactions Drive the Stereoselectivity of Silylium-Ion Asymmetric Counteranion-Directed Catalysis
Stacking and Electrostatic Interactions Drive the Stereoselectivity of Silylium-Ion Asymmetric Counteranion-Directed Catalysis
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DOI：
10.1002/anie.201609095
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发表时间：
2016-12-19
影响因子：
16.6
通讯作者：
Wheeler, Steven E.
中科院分区：
文献类型：
--
作者：
Seguin, Trevor J.;Wheeler, Steven E.
计算分析表明，不对称的路易斯酸有机催化的Diels-Alder环加成环戊二烯肉桂酸酯的对映选择性产生堆积的相互作用，有利于增加的二烯的更受阻的面的亲二烯体，而静电相互作用控制的非对映选择性通过选择性稳定的内过渡态。这些结果不仅解释了这些硅离子ACDC反应的立体选择性，但也应该指导更有效的离子配对不对称有机催化剂的发展。
Computational analysis shows that the enantioselectivity of asymmetric Lewis-acid organocatalysis of the Diels-Alder cycloaddition of cyclopentadiene to cinnamates arises from stacking interactions that favor the addition of the diene to the more hindered face of the dienophile, while electrostatic interactions control the diastereoselectivity by selectively stabilizing the endo transition state. These results not only explain the stereoselectivity of these silylium-ion-ACDC reactions but should also guide the development of more effective ion-pairing asymmetric organocatalysts.