Intramolecular Anodic Olefin Coupling Reactions

这个更新项目的中心电化学介导的氧化环化反应。天然产物arteanuinn B和arteanuin M的合成将被用于探索在构建Alliacol A中所采用的合成策略的一般性，青蒿素的合成将被用于探索“Curtin-Hammett控制”环化的合成效用，异甘草酸的合成将被用于研究环化的封端引发基团的效用，并将丹卡斯特酮的合成用于确定阳极环化与引发烯烃上的吸电子基团的相容性。将继续努力扩大环化反应的范围，调整自由基阳离子的反应性，使得它们有利于碳-碳键的形成，以努力克服六元环和季碳形成的双重障碍。富电子的乙烯酮缩醛和烯胺都将被氧化，所得的自由基阳离子被烯丙基硅烷亲核试剂捕获。随后反应的产物分析将沿着使用循环伏安法来探测自由基阳离子中间体的性质以及如何操纵其随后的反应。有了这个奖项，有机和大分子化学计划支持博士的研究。华盛顿大学化学系的Moeller说。 Moeller教授和他的学生将探索利用电能诱导有机分子的选择性反应。电化学介导的反应序列将被开发，这使得所选择的有机分子的有效合成。这样的有机电化学反应提供了作为简单但高度通用的工具的承诺，用于构建形成现代药物研究基础的复杂靶结构。电化学方法也提供了潜在的“绿色”（环境友好）的有机合成方法的承诺。

This renewal project centers on electrochemically mediated oxidative cyclization reactions. Syntheses of the natural products arteanuinn B and arteanuin M will be used to explore the generality of the synthetic strategy employed in the construction of alliacol A, a synthesis of artemisolide will be used to probe the synthetic utility of "Curtin-Hammett controlled" cyclizations, a synthesis of ineleganolide will be used to study the utility of enediol initiating groups for the cyclizations, and a synthesis of dankasterone will be used to determine the compatibility of anodic cyclizations with electron-withdrawing groups on the initiating olefin. Efforts to expand the scope of the cyclization reactions will be pursued, tuning the reactivity of the radical cations so that they favor carbon - carbon bond formation in an effort to overcome the twin barriers of six-membered ring and quaternary carbon formation. Both electron-rich ketene acetals and enamines will be oxidized and the resulting radical cations trapped with allylsilane nucleophiles. Product analysis of the ensuing reactions will be used along with cyclic voltammetry to probe both the nature of radical cation intermediates and how their subsequent reactions can be manipulated.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Kevin D. Moeller of the Department of Chemistry at Washington University. Professor Moeller and his students will explore the use of electrical energy to induce selective reactions of organic molecules. Electrochemically mediated reaction sequences will be developed which allow the efficient synthesis of chosen organic molecules. Such organic electrochemical reactions offer promise as simple yet highly versatile tools for the construction of the complex target structures forming the basis of modern pharmaceutical research. Electrochemical methods also offer promise as potentially "green" (environmentally benign) approaches for organic synthesis.