The Development and Characterization of Radical Anion Clock Reactions

在有机动力学项目的支持下，Tanko博士将研究几种环丙基负离子的衰变机制。特别是，围绕一种潜在的分解模式的问题，即通过快速和不可逆的环丙烷环打开进行的机制，将在本研究中得到解决。将探索这些自由基阴离子系统作为“时钟”的潜在用途，以测量竞争的双分子过程的速率。最后，探讨了自由基阴离子反应在有机合成中的潜在应用。单电子转移（SET）是有机化学中一种重要的反应途径。通过SET过程产生的物种被称为“自由基阴离子”。它们在这种反应中的中间作用可以通过重排产物的出现来推断。Tanko博士设计了研究自由基阴离子中间体的方法，并利用这些中间体作为机制探针来获得有关竞争反应机制的详细信息。除了它们固有的机理兴趣外，自由基阴离子反应还可以用来促进可能对合成重要天然产物的结构单元有用的反应。

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.