The Development and Characterization of Radical Anion Clock Reactions

自由基阴离子钟反应的发展和表征

• 批准号: 9113448
• 负责人: James Tanko
• 金额: $ 19.11万
• 依托单位: Virginia Polytechnic Institute and State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1991
• 资助国家: 美国
• 起止时间: 1991-08-01 至 1995-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9113448&HistoricalAwards=false
• 关键词: Development; Characterization; Radical; Anion; Clock

With support from the Organic Dynamics Program, Dr. Tanko will examine the mechanism of decay of several cyclopropyl ketyl anions. In particular, questions that surround one potential mode of decomposition, i.e., a mechanism that proceeds via rapid and irreversible cyclopropane ring opening, will be addressed in this study. The potential use of these radical anion systems as "clocks" to measure the rates of competing bimolecular processes will be explored. Finally, potential applications of radical anions reactions to organic synthesis will be studied. %%% Single electron transfer (SET) provides an important reaction pathway in organic chemistry. The species that are produced via SET processes are called "radical anions". Their intermediacy in such reactions can be inferred by the appearance of rearranged products. Dr. Tanko has devised methodology for studying radical anion intermediates and for utilizing these intermediates as mechanistic probes to obtain detailed information about the mechanisms of competing reactions. In addition to their inherent mechanistic interest, radical anion reactions can be used to promote reactions that are likely to be useful for synthesizing structural units of important natural products.

在有机动力学项目的支持下，坦科博士将 研究几种环丙基酮基的衰变机理 阴离子。特别是，围绕一个潜在的问题 分解模式，即，一种机制， 快速和不可逆的环丙烷开环， 在这项研究中解决。这些自由基的潜在用途 阴离子系统作为“时钟”来测量竞争的速率， 将探索双分子过程。最后，潜力 自由基负离子反应在有机合成中的应用 将被研究。 %%% 单电子转移（SET）提供了一个重要的反应 有机化学中的路径。这些物种是通过 SET过程被称为“自由基阴离子”。他们的中介作用 在这种反应中，可以通过以下现象来推断： 重组产品。坦科博士设计了一种方法 研究自由基阴离子中间体并利用它们 中间体作为机制探针，以获得详细的 关于竞争反应机制的信息。在 除了它们固有的机理兴趣之外，自由基阴离子 反应可用于促进可能 可用于合成重要的结构单元 天然产品。