Stacking and Electrostatic Interactions Drive the Stereoselectivity of Silylium-Ion Asymmetric Counteranion-Directed Catalysis

详细信息    查看全文

• 作者：Trevor J. Seguin and Prof. Steven E. Wheeler
• 刊名：Angewandte Chemie
• 出版年：2016
• 出版时间：December 19, 2016
• 年：2016
• 卷：128
• 期：51
• 页码：16121-16125
• 全文大小：1905K
• ISSN：1521-3757

文摘

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.