Design of Homolytic Chain Reactions

自由基链反应将被设计成包括接受电子和给予电子的烷基自由基加入到富电子和缺电子的不饱和体系中。这两种自由基都是由烷基汞卤化物产生的。不饱和体系对这些自由基的反应性将通过竞争反应的产物分析来确定。证明自由基在电子转移反应中的增强反应性将是本研究的重要目标。与亲核试剂的络合已被证明可以增加烷基卤化汞的供电子能力，与顺磁性物质如硅基自由基的类似亲核溶剂络合将被用来增加电子向容易还原的分子的转移。质子化或去质子化在电子转移过程中自由基活化的概念将继续研究，特别是在芳香体系的烷基化方面。来自有机动力学项目的这笔拨款支持爱荷华州立大学罗素教授的继续工作。碳-碳键的形成是有机化学中一个相当重要的过程。引发碳碳键形成的一种方法是在碳碳双键上加入碳自由基（带有一个奇电子的三价碳）。直到最近，人们才开始大力研究这种反应的合成用途。在本研究中，将开发新的方法来促进这种加成反应。研究了碳碳双键自由基加成反应活性的尺度，为有机分子的合成提供了指导。

Free radical chain reactions will be designed involving electron- accepting and electron-donating alkyl radical additions to unsaturated systems that are both electron-rich and electron- deficient. Both types of radicals will be generated from alkylmercury halides. Reactivities of unsaturated systems toward these radicals will be established from product analysis by competitive reactions. Demonstration of enhanced reactivity in electron transfer reactions of radicals will be an important goal of this research. Complexation with nucleophiles has already been demonstrated to increase the electron-donating ability of alkylmercury halides and similar nucleophilic solvent complexation with paramagnetic species such as silyl radicals will be used to increase electron transfer to an easily reduced molecule. The concept of radical activation in electron transfer processes by protonation or deprotonation will continue to be pursued, particularly in regard to the alkylation of aromatic systems. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Russell at Iowa State University. The formation carbon-carbon bonds is a process of considerable importance in organic chemistry. One method by which the formation of carbon-carbon bonds is initiated is the addition of a carbon free radical (a trivalent carbon with one odd electron) to a carbon-carbon double bond. Only recently has the synthetic utility of this reaction been vigorously pursued. In this research, new methods will be developed to facilitate this addition reaction. A scale of reactivity of free radical addition to carbon-carbon double bonds will be developed and this will serve as a guide for the synthesis of organic molecules.