Cation Radical Explorations

阳离子自由基探索

• 批准号: 9312460
• 负责人: Joseph Dinnocenzo
• 金额: $ 25.5万
• 依托单位: University of Rochester
• 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: 1993-07-15 至 1996-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9312460&HistoricalAwards=false
• 关键词: Cation; Radical; Explorations

9312460 Dinnocenzo The generality, scope, and limitations of three-electron SN2 substitutions on cation radical sigma bonds will be studied. The study will: (1) extend the variety of nucleophiles that can be used in practical substitution reactions, (2) investigate the factors that control the regiochemistry of three-electron SN2 reactions, (3) probe the electronic structures of various cyclopropane cation radicals to test structure/reactivity relationships, and (4) test the viability of substitution reactions on simple, alkyl- substituted cyclopropane cation radicals and, in addition, cation radicals which do not contain a cyclopropane ring. %%% This grant from the Organic Dynamics Program supports the work of Professor Joseph P. Dinnocenzo at the University of Rochester. The reactions of electron-rich molecules with cyclopropane cation radicals will be studied. The latter species are three-carbon cycles in which one electron has been removed. The study will include consideration of where the electron-rich molecule attacks the cyclopropane cation radical and extension of the reaction to species other than the cyclopropane cation radical. These reactions will have the potential to make larger molecules that are of interest. The reaction to be studied will provide important theoretical insight as well, since it is the three-electron analog of a common two-electron substitution reaction. ***

9312460 Dinnocenzo三电子SN 2的一般性、范围和局限性 将研究阳离子自由基σ键上的取代。 该研究将：（1）扩大亲核试剂的种类， 可用于实际的取代反应，（2） 研究控制区域化学的因素 三电子SN 2反应，（3）探测电子 各种环丙烷阳离子自由基的结构来测试 结构/反应性关系，以及（4）测试 在简单的烷基取代的环丙烷阳离子自由基上的取代反应的可行性，此外， 不含环丙烷环的阳离子基团。 %有机动力学计划的这一赠款支持 约瑟夫P.迪诺森佐教授的工作， 罗切斯特。富电子分子与 将研究环丙烷阳离子自由基。后者 物种是三碳循环，其中一个电子具有 被移除了该研究将包括考虑在哪里 富电子分子攻击环丙烷阳离子 自由基和扩展的反应物种以外的 环丙烷阳离子自由基。这些反应将 制造更大分子的潜力。 待研究的反应将提供重要的 理论上的洞察力，以及，因为它是三电子 类似于常见的双电子取代反应。 ***