Quantitative DFT Modeling of the Enantiomeric Excess for Dioxirane-Catalyzed Epoxidations

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• 作者：Severin T. Schneebeli ; Michelle Lynn Hall ; Ronald Breslow* ; Richard Friesner*
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：March 25, 2009
• 年：2009
• 卷：131
• 期：11
• 页码：3965-3973
• 全文大小：336K
• 年卷期：v.131,no.11(March 25, 2009)
• ISSN：1520-5126

文摘

Herein we report the first fully quantum mechanical study of enantioselectivity for a large data set. We show that transition state modeling at the UB3LYP-DFT/6-31G* level of theory can accurately model enantioselectivity for various dioxirane-catalyzed asymmetric epoxidations. All the synthetically useful high selectivities are successfully “predicted” by this method. Our results hint at the utility of this method to further model other asymmetric reactions and facilitate the discovery process for the experimental organic chemist. Our work suggests the possibility of using computational methods not simply to explain organic phenomena, but also to predict them quantitatively.