Design of Homolytic Chain Reactions

自由基链式反应将被设计为涉及电子- 接受和给电子的烷基加成， 不饱和系统既富电子又电子- 不足这两种类型的自由基都将由 卤化烷基汞。不饱和体系对 这些自由基将通过产物分析来确定， 竞争反应。增强反应性的证明， 自由基的电子转移反应将是一个重要的目标 of this research研究.与亲核试剂的络合已经被 证明增加电子的能力， 卤化烷基汞和类似的亲核溶剂络合 与顺磁性物质如甲硅烷基一起， 增加电子转移到易还原分子。的 电子转移过程中自由基活化的概念 将继续进行质子化或去质子化， 特别是在芳族体系的烷基化方面。 %%% 有机动力学计划的这笔赠款支持 罗素教授在爱荷华州州立大学的继续工作。的 形成碳-碳键是一个相当大的过程， 有机化学的重要性。其中一种方法， 碳-碳键的起始是添加碳 自由基（带有一个奇数电子的三价碳）转化为 碳碳双键直到最近， 这种反应一直在积极进行。在这项研究中，新 将开发促进该加成反应的方法。一 碳-碳自由基加成反应性标度 将开发双键，这将作为指导， 有机分子的合成。

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.