Dynamic Effects on Fates of Reactive Intermediates in Synthesis and Biosynthesis

在这个由化学部化学结构、动力学机制B计划资助的项目中，加州大学戴维斯分校化学系的Dean J. Tantillo教授正在利用现代计算化学方法探索有机分子反应性的新方面。本研究的目的是建立新的机理模型，以帮助理解反应性物种的行为。所揭示的原理可能会改变有机化学家预测反应如何发生以及结构复杂的有机分子反应形成何种产物的方式。除了机械模型的根本重要性，该项目将培养学生（研究生和本科生，一些来自代表性不足的群体）在多学科方法机械化学，并让他们接触到采用这种技术的职业。此外，将开发新方法，使盲人和视障学生能够使用应用计算化学，作为鼓励这些学生在STEM领域从事职业的努力的一部分。最后，将建立一个在线资源，供教师们提供分子反应的物理合理解释。这项研究将集中在合成相关重排的不寻常势能面上。将分析和预测非统计动态效应，并构建反应性和选择性的通用模型。特别是，反应的选择性的起源，在过渡态后分叉的产物的途径将被询问。 研究人员还将研究特定静电效应对受非统计动态效应影响的反应速率控制的影响和效用。该奖项反映了NSF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。

In this project, funded by the Chemical Structure, Dynamics & Mechanism B Program of the Chemistry Division, Professor Dean J. Tantillo of the Department of Chemistry at the University of California, Davis is using modern computational chemistry methods to explore new aspects of the reactivity of organic molecules. The goal of this research is to construct new mechanistic models to help understand the behavior of reactive species. The principles uncovered may transform how organic chemists predict how reactions occur and which products form for reactions of structurally complex organic molecules. In addition to the fundamental importance of the mechanistic models , the project will train students (graduate and undergraduate, several from underrepresented groups) in multidisciplinary approaches to mechanistic chemistry and expose them to careers that employ such techniques. In addition, new methods for making applied computational chemistry accessible to blind and visually impaired students will be developed as part of an effort to encourage these students to pursue careers in STEM fields. Finally, an online resource for teachers who wish to provide physically sound depictions of molecules reacting will be established.This research will focus on unusual potential energy surfaces for synthetically relevant rearrangements. Non-statistical dynamic effects will be analyzed and predicted, and general models of reactivity and selectivity will be constructed. In particular, the origins of selectivity for reactions in which pathways to products bifurcate after transition states will be interrogated. The researchers will also examine the influence and utility of particular electrostatic effects on controlling rates for reactions subject to non-statistical dynamic effects.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.