Pushing the Limits of Reactivity Principles for Organic Reactions

在这个由化学系化学结构、动力学机制B（CSDM-B）项目资助的项目中，加州大学戴维斯分校化学系的Tantillo教授正在利用现代计算化学方法探索有机分子反应的反应性原理的极限。本研究的目的是提供基本的了解，控制反应的水平，用于预测实验室反应的结果的因素。这项研究将通过构建新的机械模型来推进机械有机化学的知识，包括那些基于非统计动态效应的模型，这些模型允许反应绕过轨道对称性约束，获得激发态的异常反应性，并利用熵来控制选择性。除了通过这项研究发现的机械模型的根本重要性，该项目将有助于培养学生（研究生和本科生，一些来自代表性不足的群体）在多学科的方法来机械化学，并使他们接触到不同的职业，采用这种技术。此外，还将开发和广泛分发教育资源，向学生讲授反应过程中的分子振动，以及使盲人和视力受损学生能够使用应用计算化学的方法。这项研究将集中在三类反应，每一个都有自己独特的挑战：显然禁止周环反应，光化学有机反应显示的行为类似于与基态后过渡态分叉的反应，和熵控制的选择性的有机反应。非统计动态效应将被分析和预测为每一个，反应性和选择性的一般模型将被构建和用于设计新的reaction.This奖项反映了NSF的法定使命，并已被认为是值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估的支持。

In this project, funded by the Chemical Structure, Dynamics & Mechanisms B (CSDM-B) Program of the Chemistry Division, Professor Tantillo of the Department of Chemistry at the University of California, Davis is using modern computational chemistry methods to explore the limits of reactivity principles for reactions of organic molecules. The goal of this research is to provide fundamental understanding of factors that control reactivity at a level useful for predicting laboratory reaction outcomes. This research will advance knowledge in mechanistic organic chemistry through the construction of new mechanistic models, including those based on non-statistical dynamic effects that allow reactions to circumvent orbital symmetry constraints, access unusual reactivity of excited states and utilize entropy to control selectivity. In addition to the fundamental importance of the mechanistic models uncovered through this research, the project will serve to train students (graduate and undergraduate, several from underrepresented groups) in multidisciplinary approaches to mechanistic chemistry and expose them to diverse careers that employ such techniques. In addition, educational resources for teaching students about molecular vibrations during reactions, and methods for making applied computational chemistry accessible to blind and visually impaired students, will be developed and widely distributed. This research will focus on three classes of reactions, each with its own unique challenges: apparently forbidden pericyclic reactions, photochemical organic reactions displaying behavior akin to that of reactions with ground state post-transition state bifurcations, and organic reactions with entropy-controlled selectivity. Non-statistical dynamic effects will be analyzed and predicted for each, and general models of reactivity and selectivity will be constructed and used to design new reactions.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.