Modern Theoretical Carbocation Chemistry

现代理论碳正离子化学

基本信息

批准号：
1565933
负责人：
Dean Tantillo
金额：
$ 48万
依托单位：
University of California-Davis
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2016
资助国家：
美国
起止时间：
2016-06-01 至 2019-05-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1565933&HistoricalAwards=false
关键词：
Modern Theoretical Carbocation Chemistry

项目摘要

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.

NSF 化学部的化学结构、动力学和机理项目支持加州大学戴维斯分校化学系 Dean Tantillo 教授的研究。 Tantillo 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性的新原理。所揭示的原理改变了有机化学家预测产生复杂分子的许多反应的机制和产物分布的方式。除了通过这项研究发现的机械模型的根本重要性之外，该项目还用于培训来自不同背景的学生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职业。此外，我们正在开发新方法，让盲人和视障学生能够接触到应用计算化学，作为鼓励该群体在 STEM 领域追求职业的努力的一部分。这项研究的结果部分是通过与当地植物园合作的外展计划来传播的。这项研究通过构建碳正离子反应性的详细机制模型来推进机械有机化学的知识。特别是，对碳正离子重排的异常势能表面进行了表征，对碳正离子行为的非统计动态效应进行了分析和预测，并将反应性模型推向了新反应的设计和测试。该项目的具体目标是：（1）阐明控制涉及多个异步事件的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预测其产物分布实验室实验。 (3) 将茶酶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。

项目成果

期刊论文数量（3）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Source of Rate Acceleration for Carbocation Cyclization in Biomimetic Supramolecular Cages

仿生超分子笼中碳正离子环化速率加速的来源

DOI：
10.1021/jacs.2c04179
发表时间：
2022-06
期刊：
Journal of the American Chemical Society
影响因子：
15
作者：
Nguyen, Quynh Nhu;Xia, Kay T.;Zhang, Yue;Chen, Nanhao;Morimoto, Mariko;Pei, Xiaokun;Ha, Yang;Guo, Jinghua;Yang, Wanli;Wang, Lee;et al
通讯作者：
et al

Designing Reactions with Post-Transition-State Bifurcations: Asynchronous Nitrene Insertions into C–C σ Bonds

设计具有后过渡态分岔的反应：异步氮烯插入 C–C– 键