Experimental and Theoretical Investigations of Organic Reaction Rates and Mechanisms

有机反应速率和机理的实验和理论研究

• 批准号: 9616772
• 负责人: Kendall Houk
• 金额: $ 57.96万
• 依托单位: University of California-Los Angeles
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1997
• 资助国家: 美国
• 起止时间: 1997-01-01 至 1999-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9616772&HistoricalAwards=false
• 关键词: Experimental; Theoretical; Investigations; Organic; Reaction

Dr. Kendall N. Houk, of the Department of Chemistry at the University of California, Los Angeles, is supported by the Organic Dynamics Program to carry out experimental and theoretical investigations of organic reaction rates and mechanisms. Using several levels of theory, but with particular focus on density functional theory (DFT), Dr. Houk will examine a number of problems of chemical and biological importance, including the femtosecond dynamics of pericyclic reactions, the stereoselectivity and isotope effects in vinylcyclopropane-cyclopentene rearrangements, the dynamics and anomalous activation parameters of carbene rearrangements, and aromaticity and bond localization in cyclocarbons and novel non-alternant polycyclic aromatics and anti-aromatics. Studies of the origins of stereoselectivity in biradical reactions and of the use of DFT to probe biradical surfaces will also be carried out. Explorations of biological catalysis and transition structures in enzyme- and antibody-catalyzed reactions will lead to the development of synthetic enzyme mimics. Theory and experiment play symbiotic roles in chemistry - experiments lead to new observations, theoretical work is often required in order to develop an understanding of these observations, and the resulting theories then often lead to proposals for additional experimentation in order to test their validity. Professor Houk and his collaborators will direct theoretical and experimental studies toward the elucidation of a number of central reaction processes in organic and biological chemistry, including the complex issue of how enzymes effect chemical transformations. These studies will lead not only to a fundamental level of understanding of these important processes, but also to the discovery of new reaction chemistry predicated on the theoretical findings. The studies of biological systems, for example, will lead to the development of synthetic enzyme equivalents, compounds designed and synthesized to effect chosen molecular transformations in a highly selective manner.

加州大学洛杉矶分校化学系的肯德尔·n·霍克博士得到了有机动力学项目的支持，对有机反应速率和机理进行实验和理论研究。Houk博士将使用几个层次的理论，但特别侧重于密度泛函数理论（DFT），研究一些重要的化学和生物学问题，包括周环反应的飞秒动力学，乙烯基环丙烷-环戊烯重排的立体选择性和同位素效应，碳重排的动力学和异常活化参数，环碳化合物和新型非交替多环芳烃和反芳烃的芳香性和键定位。研究双基反应中立体选择性的起源和使用DFT探测双基表面也将进行。对酶和抗体催化反应的生物催化和过渡结构的探索将导致合成酶模拟物的发展。理论和实验在化学中扮演着共生的角色——实验导致新的观察结果，通常需要理论工作来发展对这些观察结果的理解，然后产生的理论通常会导致对额外实验的建议，以测试其有效性。Houk教授和他的合作者将指导理论和实验研究，以阐明有机和生物化学中的一些中心反应过程，包括酶如何影响化学转化的复杂问题。这些研究不仅将导致对这些重要过程的基本理解，而且还将发现基于理论发现的新的反应化学。例如，对生物系统的研究将导致合成酶等同物的发展，设计和合成的化合物以高度选择性的方式影响选定的分子转化。