Pushing the Limits of Reactivity Principles for Organic Reactions

突破有机反应反应原理的极限

基本信息

批准号：
2154083
负责人：
Dean Tantillo
金额：
$ 48.98万
依托单位：
University of California-Davis
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2022
资助国家：
美国
起止时间：
2022-07-01 至 2025-06-30
项目状态：
未结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154083&HistoricalAwards=false
关键词：
Pushing Limits Reactivity Principles Organic

项目摘要

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.

在这个项目中，由化学部化学结构、动力学和机理 B (CSDM-B) 项目资助，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来探索有机分子反应的反应原理。这项研究的目标是提供对控制反应性的因素的基本了解，这些因素可用于预测实验室反应结果。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之外，该项目还将用于培训学生（研究生和本科生，其中一些来自代表性不足的群体）采用机械化学的多学科方法，并使他们接触到采用此类技术的不同职业。此外，还将开发并广泛分发用于向学生讲授反应过程中分子振动的教育资源，以及向盲人和视障学生提供应用计算化学的方法。这项研究将重点关注三类反应，每类反应都有其独特的挑战：明显禁止的周环反应、表现出类似于基态后过渡态分叉反应行为的光化学有机反应，以及具有熵控制选择性的有机反应。将分析和预测每个反应的非统计动态效应，并将构建反应性和选择性的通用模型并用于设计新的反应。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值进行评估，被认为值得支持以及更广泛的影响审查标准。