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

有机动力学计划的这笔赠款为以下方面提供支持： William Dolbier博士的持续研究 佛罗里达大学。这项研究的主旨是研究 氟独特的动力学和热力学效应 取代基的热均裂机制， 周环反应 设计的实验将提供一个基本的 了解以前观察到的戏剧性的起源 取代基效应其中包括旨在测试 取代基质量对转动分量的影响 在碳-碳键断裂过程中赋予的，并且测试所述碳-碳键的断裂。 电循环热力学调节的可行性 均衡 创新的机械探头，如高 压力技术，动力学同位素效应，立体化学 探针，溶剂效应研究和理论与 实验将被用来研究的机制， 电环化反应，（2+2），（2+4）和1，3-偶极 环加成和许多涉及均裂的反应 形成双自由基。

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.