Intramolecular Anodic Olefin Coupling Reactions

这项研究致力于开发新的方法， 通过氧化官能化的 二烯的电化学方法。初步结果表明 五元、六元和七元环可以在高分子中形成， 通过这种方法。这些研究涉及设计， 一系列偶联物的合成及电化学氧化 基板旨在探测的整体要求， 反应这些实验旨在检查 引发和终止偶联反应 与反应条件相容的基团， 可以形成的环的大小， 取代基，产物的立体化学，以及 反应条件对产物形成的影响。 最后，该项目检查了 用于构建多环体系的反应， 引发串联环化反应。 %%% 有了这个奖项，化学合成有机计划 该部门将支持凯文·D博士的研究穆勒 华盛顿大学化学系。的 该项目是在综合方法的一般领域， 重点是碳-碳键形成的发展， 用电化学方法氧化官能化的二烯 方法.这些类型的反应极其重要 因为它们允许开发全新的路线， 分子合成氧化有机电化学是 非常适合于引发这些反应中的关键步骤 因为它可以选择性地产生活性中间体， 中性条件。

This research addresses the development of new approaches to carbon-carbon bond formation by oxidation of functionalized dienes using electrochemistry. Preliminary results indicate that five, six and seven-membered rings can be formed in high yield by this methodology. The studies involve the design, synthesis and electrochemical oxidation of a series of coupling substrates aimed at probing the overall requirements of the reaction. These experiments are designed to examine the coupling reactions involving the initiating and terminating groups that are compatible with the reaction conditions, the size of the rings that can be formed, the effect of substituents, the stereochemistry of the products, and the effect of the reaction conditions on product formation. Finally, the project examines the synthetic utility of the reactions for constructing polycyclic ring systems and initiating tandem cyclization reactions. %%% With this award, the Synthetic Organic Program of the Chemistry Division will support the research of Dr. Kevin D. Moeller of the Department of Chemistry at Washington University. The project is in the general area of synthetic methodology and focusses on the development of carbon-carbon bond formation by oxidation of functionalized dienes using electrochemical methods. These types of reactions are extremely important because they allow the development of entirely new routes for molecular synthesis. Oxidative organic electrochemistry is ideally suited for initiating the key step in these reactions since it can selectively generate reactive intermediates under neutral conditions.