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

有机动力学计划中的这笔赠款为佛罗里达大学的威廉·多尔比尔博士的继续研究提供了支持。这项研究的重点是研究氟取代基对热均解和周环反应机理的独特的动力学和热力学效应。已经设计的实验将提供对先前观察到的戏剧性取代基效应的起源的基本理解。包括旨在测试取代基质量对碳-碳键断裂时提供的转动分量的影响的实验，以及调节电循环平衡热力学的可行性的测试。创新的机理探针，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，将被用来研究电环反应、(2+2)、(2+4)和1，3-偶极环加成反应以及一些涉及双自由基均解生成的反应的机理。

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.