Exploring and Understanding the Effect of Cation-Pi Interactions in Asymmetric Catalysis

探索和理解阳离子-Pi 相互作用在不对称催化中的作用

• 批准号: 1856772
• 负责人: Sheryl Wiskur
• 金额: $ 45万
• 依托单位: University of South Carolina at Columbia
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-07-01 至 2023-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1856772&HistoricalAwards=false
• 关键词: Exploring; Understanding; Effect; Cation; Pi

In this project, funded by the Chemical Structure, Dynamics and Mechanisms-B Program of the Chemistry Division, Professor Sheryl Wiskur of the Department of Chemistry and Biochemistry at the University of South Carolina is attempting to understand how intermolecular interactions control chemical reactions in order to rationally design catalysts. Optically active intermediates are of increasing in importance in the pharmaceutical and agrochemical industries. New approaches to obtaining these commercially important compounds are constantly being developed. It is important to understand the interactions that aid in achieving selective product formation in order to rationally design catalysts. This research investigates how the intermolecular interactions, termed a cation-pi interactions, are involved in controlling selectivity. The research could aid the development of more efficient asymmetric catalysts, which are needed in drug development and the manufacture of many other chemicals. The project also takes into account the valuable training graduate students receive while carrying out the experiments to understand this supramolecular interaction. Broader impacts include the mentoring of women scientists to aid in retaining women in science.Delocalized cations are often proposed to aid in controlling asymmetric reactions through cation-pi interactions between the substrate and catalyst, yet delocalized cations have not been as widely studied. This project explores this supramolecular interaction in two ways. The thermodynamics of binding of four common organocatalyst core structures will be studied. The team will also investigate how the binding trends relate to the rate and selectivity of a model reaction as electronics on the pi system are altered. The electrostatics of binding are explored computationally to understand binding orientations and localization of charge. The electronic changes in the cation (i.e., substituted catalysts) are examined to understand how those changes affect the same model reaction in terms of thermodynamics, kinetics, and selectivity.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

南卡罗来纳大学化学与生物化学系的Sheryl Wiskur教授在化学结构、动力学和机理b项目的资助下，试图了解分子间相互作用如何控制化学反应，从而合理设计催化剂。旋光性中间体在制药和农化工业中越来越重要。获取这些具有重要商业价值的化合物的新方法不断被开发出来。为了合理设计催化剂，了解有助于实现选择性产物形成的相互作用是很重要的。本研究探讨分子间相互作用，称为阳离子- π相互作用，是如何参与控制选择性的。这项研究有助于开发更有效的不对称催化剂，这在药物开发和许多其他化学品的制造中都是必需的。该项目还考虑到研究生在进行实验以理解这种超分子相互作用时所接受的宝贵训练。更广泛的影响包括为女科学家提供指导，以帮助留住女性从事科学工作。离域阳离子通常被认为是通过底物和催化剂之间的阳离子- π相互作用来帮助控制不对称反应，但离域阳离子尚未得到广泛的研究。这个项目从两个方面探索了这种超分子相互作用。研究了四种常见有机催化剂核心结构的结合热力学。该团队还将研究当π系统上的电子发生改变时，结合趋势与模型反应的速率和选择性之间的关系。通过计算探讨了结合的静电力学，以了解结合的方向和电荷的定位。检查阳离子（即取代催化剂）中的电子变化，以了解这些变化如何在热力学，动力学和选择性方面影响相同的模型反应。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Exploration of silicon phthalocyanines as viable photocatalysts for organic transformations

• DOI: 10.1016/j.jphotochem.2021.113547
• 发表时间: 2022-01
• 期刊: Journal of Photochemistry and Photobiology A: Chemistry
• 作者: Shelby D. Dickerson;P. Ayare;Aaron K. Vannucci;S. L. Wiskur

Mechanistic investigations of alcohol silylation with isothiourea catalysts

异硫脲催化剂醇硅烷化反应的机理研究

• DOI: 10.1039/d1ob01732b
• 发表时间: 2021
• 期刊: Organic & Biomolecular Chemistry
• 影响因子: 3.2
• 作者: Redden, Brandon K.;Clark, Robert W.;Gong, Ziyuan;Rahman, Md. Mamdudur;Peryshkov, Dmitry V.;Wiskur, Sheryl L.
• 通讯作者: Wiskur, Sheryl L.