Radical Ion Rearrangements - Principles and Applications

自由基离子重排 - 原理和应用

• 批准号: 0108907
• 负责人: James Tanko
• 金额: $ 32.1万
• 依托单位: Virginia Polytechnic Institute and State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-08-15 至 2005-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0108907&HistoricalAwards=false
• 关键词: Radical; Ion; Rearrangements; Principles; Applications

With the support of the Organic and Macromolecular Chemistry Program, Professor James M. Tanko, of the Department of Chemistry at Virginia Polytechnic Institute and State University, is studying the principals and applications of radical ion rearrangements. Professor Tanko is exploring the structural features which govern the rate of rearrangement of radical anions derived from carbonyl compounds as well as the influence of solvent and counterion on these rearrangement reactions. Study of the oxidation potentials of cyclopropyl- and cyclobutylamines and determination of rate constants for the ring opening reactions of radical cations generated from their oxidation may shed light on the biological oxidations catalyzed by monoamine oxidase. Both electrochemical and laser flash photolysis methods will be used to generate the desired ions. Information regarding the driving force for ring opening will be obtained from appropriately constructed thermodynamic cycles, while theoretical methods will be used to provide information regarding the structure of radical ions and to estimate thermodynamic properties in situations where such information cannot be obtained experimentally.Molecules bearing both a net charge (either positive or negative) and an unpaired electron appear as key intermediates in many chemical and biological processes. Development of an understanding of the structure and dynamics of these so-called radical cations and anions is central to elucidation of the fundamental details of how such processes occur. With the support of the Organic and Macromolecular Chemistry Program, Professor James M. Tanko, of the Department of Chemistry at Virginia Polytechnic Institute and State University, is carrying out studies of the preparation, structure, and reaction chemistry of radical anions and radical cations. Through a combination of experimental and theoretical approaches, Professor Tanko is shedding light on the nature of these elusive intermediates, addressing fundamental issues of organic reaction mechanism and leading to a deeper understanding of the function of biological catalysts such as monoamine oxidase.

在有机化学和高分子化学项目的支持下，弗吉尼亚理工学院和州立大学化学系的詹姆斯·M·坦科教授正在研究自由基离子重排的原理和应用。Tanko教授正在探索支配来自羰基化合物的自由基阴离子重排速度的结构特征，以及溶剂和反离子对重排反应的影响。研究环丙胺和环丁胺的氧化电位，并测定其氧化生成的自由基阳离子开环反应的速率常数，可能有助于揭示单胺氧化酶催化的生物氧化反应。电化学和激光闪光光解方法将被用来产生所需的离子。有关开环驱动力的信息将从适当构建的热力学循环中获得，而理论方法将用于提供有关自由基离子结构的信息，并在无法通过实验获得此类信息的情况下估计热力学性质。同时具有净电荷(正电荷或负电荷)和未配对电子的分子在许多化学和生物过程中似乎是关键的中间体。了解这些所谓的自由基阳离子和阴离子的结构和动力学，对于阐明这些过程如何发生的基本细节是至关重要的。在有机化学和高分子化学计划的支持下，弗吉尼亚理工学院和州立大学化学系的詹姆斯·M·坦科教授正在开展自由基阴离子和自由基阳离子的制备、结构和反应化学的研究。通过实验和理论相结合的方法，Tanko教授揭示了这些难以捉摸的中间体的性质，解决了有机反应机理的基本问题，并导致对单胺氧化酶等生物催化剂的功能有了更深的理解。