Bicyclic Guanidine-Catalyzed Asymmetric Cycloaddition Reaction of Anthrones—Bifunctional Binding Modes and Origin of Stereoselectivity,The Journal of Organic Chemistry

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Bicyclic Guanidine-Catalyzed Asymmetric Cycloaddition Reaction of Anthrones—Bifunctional Binding Modes and Origin of Stereoselectivity
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-11-11 , DOI: 10.1021/acs.joc.0c02008
Choon Wee Kee _{1,

2} , Ming Wah Wong ₃

Affiliation

We report a computational analysis of the [5,5] bicyclic guanidine-catalyzed asymmetric cycloaddition reaction of anthrones. Based on extensive conformational search of key intermediates and transition states on the potential energy surface and density functional theory calculations, we studied five plausible binding modes between the guanidine catalyst and substrates for this reaction. Our results indicate that the most favorable pathway is a stepwise conjugate addition-Aldol sequence via the dual hydrogen-bond binding mode. The predicted level of enantioselectivity is in good agreement with experimental values. Trends in variation of substrates and catalysts have also been reproduced by our calculations. Decomposition analysis revealed the significance of aromatic interactions in stabilizing the key enantioselectivity-determining transition state structures.

中文翻译：

蒽的双环胍催化的不对称环加成反应—双功能结合方式和立体选择性的起源

我们报告了蒽环[5,5]双环胍催化的不对称环加成反应的计算分析。在势能表面和密度泛函理论计算的关键中间体和过渡态的广泛构象搜索基础上，我们研究了胍催化剂与底物之间五种可能的结合模式。我们的结果表明，最有利的途径是通过双氢键结合模式的逐步共轭加成-Aldol序列。对映选择性的预测水平与实验值非常吻合。底物和催化剂变化的趋势也通过我们的计算得到了再现。

更新日期：2020-12-04

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