Kinetic and Stereochemical Effects of Substituents in Thermal Homolytic and Pericyclic Reactions

这项有机动力学项目的拨款为佛罗里达大学的William Dolbier博士的持续研究提供了支持。本研究的重点是研究氟取代基对热均溶反应和周环反应机理的独特动力学和热力学效应。已设计的实验将对先前观察到的戏剧性取代基效应的起源提供基本的理解。包括旨在测试取代基质量对碳-碳键裂解过程中传递的旋转成分的影响的实验，以及调整电环平衡热力学的可行性测试。创新的机制探针，如高压技术、动力学同位素效应、立体化学探针、溶剂效应研究和理论与实验的关联，将被用于研究电环反应、（2+2）、（2+4）和1,3-偶极环加成以及一些涉及双自由基均溶形成的反应的机理。

This grant in the Organic Dynamics Program provides support for the continuing research of Dr. William Dolbier of the University of Florida. The thrust of the research is the study of the unique kinetic and thermodynamic effects of fluorine substituents on the mechanisms of thermal homolytic and pericyclic reactions. Experiments have been designed which will provide a fundamental understanding of the origin of the previously observed dramatic substituent effects. Included are experiments designed to test the influence of substituent mass upon the rotational component imparted during carbon-carbon bond cleavage and a test of the feasibility of tuning the thermodynamics of electrocyclic equilibria. Innovative mechanistic probes such as high pressure techniques, kinetic isotope effects, stereochemical probes, solvent effect studies and correlation of theory with experiment will be employed to study the mechanisms of electrocyclic reactions, (2+2), (2+4) and 1,3-dipolar cycloadditions and a number of reactions involving homolytic formation of diradicals.