Mechanistic Insights into Bicyclic Guanidine-Catalyzed Reactions from Microscopic and Macroscopic Perspectives,The Journal of Organic Chemistry

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Mechanistic Insights into Bicyclic Guanidine-Catalyzed Reactions from Microscopic and Macroscopic Perspectives
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2015-05-22 00:00:00 , DOI: 10.1021/acs.joc.5b00709
Hansong Xue ₁ , Danfeng Jiang ₁ , Huan Jiang ₁ , Choon Wee Kee ₁ , Hajime Hirao ₁ , Takahiro Nishimura ₂ , Ming Wah Wong ₃ , Choon-Hong Tan ₁

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Chiral bicyclic guanidine can act as an efficient chiral Brønsted base catalyst in enantioselective reactions, delivering good yields with high enantioselectivities. There is interest in understanding the detailed mechanisms of these guanidine-catalyzed reactions. Herein, we performed a detailed kinetic study of three different types of chiral bicyclic guanidine-catalyzed reactions, determining the bifunctionality of our guanidine catalyst. Although these three reactions share a similar catalytic cycle, their intrinsic kinetic behaviors are significantly different from each other because of the difference in the rate-determining step. The calculated theoretical rate expression for each reaction, as a result of the mechanism elucidated with density functional theory calculations, agrees well with the respective experimentally observed rate equation.

中文翻译：

从微观和宏观的角度看待双环胍催化的反应机理。

手性双环胍可以作为对映选择性反应中的有效手性布朗斯台德碱催化剂，以高对映选择性提供良好的收率。有兴趣了解这些胍催化的反应的详细机理。在本文中，我们对三种不同类型的手性双环胍催化的反应进行了详细的动力学研究，确定了我们的胍催化剂的双功能性。尽管这三个反应共享相似的催化循环，但由于速率确定步骤的不同，它们的内在动力学行为彼此之间也存在显着差异。通过密度泛函理论计算阐明的机理，计算出的每个反应的理论速率表达式与各自实验观察到的速率方程式非常吻合。

更新日期：2015-05-22

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