Design of Homolytic Chain Reactions

均裂链式反应的设计

• 批准号: 9220639
• 负责人: Glen Russell
• 金额: $ 32.4万
• 依托单位: Iowa State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1993
• 资助国家: 美国
• 起止时间: 1993-01-01 至 1997-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9220639&HistoricalAwards=false
• 关键词: Design; Homolytic; Chain; Reactions

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.

自由基链式反应的设计涉及将受电子和供电子烷基自由基加成到富电子和缺电子的不饱和体系中。两种类型的自由基均由烷基卤化汞产生。不饱和系统对这些自由基的反应活性将通过竞争反应的产物分析来确定。证明自由基电子转移反应的反应活性增强将是本研究的一个重要目标。与亲核试剂的络合已被证明可以增加烷基卤化汞的给电子能力，并且类似的亲核溶剂与顺磁性物质（例如甲硅烷基自由基）的络合将用于增加电子转移到易于还原的分子。通过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被研究，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立大学的持续工作。碳-碳键的形成是有机化学中相当重要的过程。引发碳-碳键形成的一种方法是将碳自由基（具有一个奇数电子的三价碳）加成到碳-碳双键上。直到最近，该反应的合成应用才得到大力发展。在这项研究中，将开发新方法来促进这种加成反应。将开发自由基加成碳-碳双键的反应性尺度，这将作为有机分子合成的指南。