Modern Theoretical Carbocation Chemistry

NSF化学部的化学结构、动力学和机理计划支持加州大学戴维斯分校化学系迪恩·坦蒂洛教授的研究。坦蒂洛教授和他的学生正在使用现代计算化学方法来探索控制化学反应的新原理。揭示的原理改变了有机化学家预测导致复杂分子的许多反应的机理和产物分布的方式。除了通过这项研究发现的机械模型的基本重要性外，该项目还用于培训来自不同背景的学生采用多学科方法学习机械化学，并使他们接触到使用这种技术的职业。此外，正在开发使盲人和视障学生能够接触到应用计算化学的新方法，作为鼓励这一群体在STEM领域追求职业生涯的努力的一部分。这项研究的结果部分是通过与当地植物园合作的推广计划来传播的。这项研究通过构建碳正离子反应的详细机理模型来促进机械有机化学方面的知识。特别是，表征了碳正离子重排的异常势能面，分析和预测了碳正离子行为的非统计动态效应，并将反应性模型推广到新反应的设计和测试。这个项目的具体目标是：(1)阐明控制参与多个异步事件协同反应的物种动力学行为的一般原理(2)设计具有后过渡态分叉的反应，并在实验室实验之前预测其产物分布。(3)将Theozyme动力学方法发展成为理解和设计利用相对较弱的非共价相互作用的催化剂的工具。

The Chemical Structure, Dynamics and Mechanism Program of the NSF Chemistry Division supports the research of Professor Dean Tantillo in the Department of Chemistry at The University of California-Davis. Professor Tantillo and his students are using modern computational chemistry methods to explore new principles governing chemical reactivity. The principles uncovered transform how organic chemists predict mechanisms and product distributions for many reactions that lead to complex molecules. In addition to the fundamental importance of the mechanistic models uncovered through this research, the project is used to train students from diverse backgrounds 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 are being developed as part of an effort to encourage this group to pursue careers in STEM fields. The results of this research are disseminated, in part, via an outreach program in partnership with a local arboretum.This research advances knowledge in mechanistic organic chemistry through the construction of detailed mechanistic models for carbocation reactivity. In particular, unusual potential energy surfaces for carbocation rearrangements are characterized, non-statistical dynamic effects on carbocation behavior are analyzed and predicted, and models of reactivity are pushed through to the design and testing of new reactions. The specific goals of this project are: (1) To elucidate general principles for controlling the dynamical behavior of species involved in concerted reactions with multiple asynchronous events (2) To design a reaction with a post-transition state bifurcation and predict its product distribution ahead of laboratory experiments. (3) To develop the theozyme dynamics approach into a tool for understanding and designing catalysts that make use of relatively weak noncovalent interactions.