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酮基阴离子的衰变机理。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环丙烷开环进行的机制，将在这项研究中得到解决。这些自由基阴离子系统作为“时钟”来测量相互竞争的双分子过程的速率的潜在用途将被探索。最后，对自由基阴离子反应在有机合成中的潜在应用进行了研究。%单电子转移(SET)反应是有机化学中重要的反应途径。通过设定过程产生的物种被称为“自由基阴离子”。它们在这类反应中的中介作用可以从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，并将这些中间体用作机械探针，以获得关于竞争反应机理的详细信息。除了其固有的机理兴趣，自由基阴离子反应还可以用于促进反应，这些反应可能有助于合成重要的天然产物的结构单元。

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.