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Mechanistic Studies of Organic Reactivity

有机反应机理研究

基本信息

批准号：
2054395
负责人：
Jeehiun Lee
金额：
$ 47万
依托单位：
Rutgers University New Brunswick
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2021
资助国家：
美国
起止时间：
2021-07-01 至 2024-06-30
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2054395&HistoricalAwards=false
关键词：
Mechanistic Studies Organic Reactivity

项目摘要

Professor Jeehiun Katherine Lee of the Department of Chemistry at Rutgers University will utilize funding provided by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division to explore organic reactivity and mechanism. One major focus will be on the complementary polarities of reactants in chemical reactions. This is commonly referred to as nucleophilicity ("seeking nuclei") or electrophilicity ("seeking electrons"). The nucleophilicity and electrophilicity of diverse reactants will be examined in the gas phase, with the ultimate goal of creating a scale to better understand fundamental reactivity. A second focus will be on reactions catalyzed by N-heterocyclic carbenes (NHCs). NHCs are novel organic substances, which have been shown to act as catalysts for a broad range of important synthetic reactions. Mechanisms for these reactions are poorly understood. In both aims, chemical reactions will be studied through a combination of computational models and experiments. Experimental studies are carried out in the gas phase, using a mass spectrometer. The absence of solvent allows for inherent reactivity to be revealed. This project has the potential to establish reactivity patterns for a wide range of organic species and improve the utility of NHCs as catalysts in chemical synthesis. Improved synthetic methods in turn impact many areas of chemistry, including making pharmaceuticals and other useful chemicals. These fundamental mechanistic studies also provide educational opportunities for both undergraduate and graduate scientists. The project provides mentoring and training for groups underrepresented in science as well.Gas phase experimental (mass spectrometric) and computational (quantum mechanical) methods are used to interrogate the properties and reactivities of species of organochemical significance. Specifically, a number of hypotheses centered on nucleophilicity, electrophilicity, reactivity, and catalysis will be tested. One objective is the development of a gas-phase scale for nucleophilicity and electrophilicity of substrates (including N-heterocyclic carbenes (NHCs)); the second objective is to gain insight into the mechanism by which NHCs catalyze synthetically important reactions. These studies will ultimately aid in the development of processes involving hydrogen activation, organocatalysis and synthesis. The work will have societal impact in terms of the education of undergraduate and graduate students, including students from underrepresented groups, and publication of research that increases fundamental chemical understanding.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.

罗格斯大学化学系的Jeehiun Katherine Lee教授将利用化学系化学结构、动态和机制B计划提供的资金来探索有机反应性和机理。一个主要的焦点将是化学反应中反应物的互补极性。这通常被称为亲核性(“寻找原子核”)或亲电性(“寻找电子”)。将在气相中检查不同反应物的亲核性和亲电性，最终目标是建立一个更好地了解基本反应性的标度。第二个重点将放在N-杂环卡宾(NHCs)催化的反应上。NHC是一种新型的有机物质，已被证明是一系列重要的合成反应的催化剂。人们对这些反应的机制知之甚少。在这两个目标中，将通过计算模型和实验相结合的方式来研究化学反应。利用质谱仪在气相中进行了实验研究。由于没有溶剂，可以显露出内在的反应性。该项目有可能建立广泛的有机物种的反应模式，并提高NHCS在化学合成中作为催化剂的用途。改进的合成方法反过来又影响到化学的许多领域，包括制造药物和其他有用的化学品。这些基础机械研究也为本科生和研究生科学家提供了教育机会。该项目还为科学中代表性不足的群体提供指导和培训。使用气相实验(质谱学)和计算(量子力学)方法来询问具有有机化学意义的物种的性质和反应性。具体地说，将测试一些以亲核性、亲电性、反应性和催化为中心的假设。一个目标是开发用于底物(包括N-杂环卡宾(NHCS))亲核性和亲电性的气相标尺；第二个目标是了解NHCS催化合成重要反应的机理。这些研究最终将有助于开发涉及氢活化、有机催化和合成的过程。这项工作将在教育本科生和研究生，包括来自代表性不足的群体的学生，以及出版增加基础化学理解的研究方面产生社会影响。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标准进行评估，被认为值得支持。

项目成果

期刊论文数量（5）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Gas-Phase Experimental and Computational Studies of 5-Halouracils: Intrinsic Properties and Biological Implications

DOI：
10.1021/acs.joc.1c00183
发表时间：
2021-04-23
期刊：
JOURNAL OF ORGANIC CHEMISTRY
影响因子：
3.6
作者：
Krajewski, Allison E.;Lee, Jeehiun K.
通讯作者：
Lee, Jeehiun K.

Gas‐phase experimental and computational studies of human hypoxanthine‐guanine phosphoribosyltransferase substrates: Intrinsic properties and biological implications

人次黄嘌呤鸟嘌呤磷酸核糖基转移酶底物的气相实验和计算研究：内在特性和生物学意义

DOI：
10.1002/poc.4343
发表时间：
2022
期刊：
Journal of Physical Organic Chemistry
影响因子：
1.8
作者：
Zhang, Lanxin;Hinz, Damon J.;Kiruba, George Sebastina;Ding, Xiao;Lee, Jeehiun K.
通讯作者：
Lee, Jeehiun K.

Mass spectrometry in organic and bio‐organic catalysis: Using thermochemical properties to lend insight into mechanism

有机和生物有机催化中的质谱分析：利用热化学性质深入了解机理