Dynamic Effects on Fates of Reactive Intermediates in Synthesis and Biosynthesis

合成和生物合成中反应中间体命运的动态影响

基本信息

批准号：
1856416
负责人：
Dean Tantillo
金额：
$ 50万
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：
2019
资助国家：
美国
起止时间：
2019-07-01 至 2022-06-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1856416&HistoricalAwards=false
关键词：
Dynamic Effects Fates Reactive Intermediates

项目摘要

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.

在该项目中，由化学部化学结构、动力学与机理B项目资助，加州大学戴维斯分校化学系Dean J. Tantillo教授正在利用现代计算化学方法探索反应性的新方面的有机分子。这项研究的目标是构建新的机制模型以帮助理解活性物质的行为。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有机分子的反应会形成哪些产物的方式。除了机械模型的根本重要性之外，该项目还将对学生（研究生和本科生，其中一些来自代表性不足的群体）进行机械化学多学科方法的培训，并使他们接触到采用此类技术的职业。此外，还将开发新方法，使盲人和视障学生能够接触到应用计算化学，作为鼓励这些学生在 STEM 领域追求职业的努力的一部分。最后，将为那些希望提供分子反应的物理声音描述的教师建立一个在线资源。这项研究将重点关注用于合成相关重排的不寻常的势能表面。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，过渡态后产物途径分叉的反应选择性的起源将受到质疑。研究人员还将研究特定静电效应对控制受非统计动态效应影响的反应速率的影响和效用。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查进行评估，被认为值得支持标准。

项目成果

期刊论文数量（23）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Synthesis and Application of Constrained Amidoboronic Acids Using Amphoteric Boron-Containing Building Blocks

两性含硼砌块约束酰胺基硼酸的合成及应用

DOI：
10.1021/acs.joc.1c02015
发表时间：
2022-01
期刊：
The Journal of Organic Chemistry
影响因子：
0
作者：
Soor, Harjeet S.;Diaz, Diego B.;Tsui, Ka Yi;Calvopiña, Karina;Bielinski, Marcin;Tantillo, Dean J.;Schofield, Christopher J.;Yudin, Andrei K.
通讯作者：
Yudin, Andrei K.

Divergent stereochemical outcomes in the insertion of donor/donor carbenes into the C–H bonds of stereogenic centers

将供体/供体卡宾插入立体中心的 C–H 键时产生不同的立体化学结果