Intramolecular Anodic Olefin Coupling Reactions

这个更新项目的中心是电化学介导的氧化环化反应。天然产物青蒿素B和青蒿素M的合成将用于探索构建蒜素A所采用的合成策略的通用性，青蒿素的合成将用于探索“Curtin-Hammett控制”的环化反应的合成用途，ineleganolide的合成将用于研究烯二醇引发基团对环化反应的应用，丹参酮的合成将用于确定阳极环化反应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，使其有利于碳-碳键的形成，以努力克服六元环和季碳形成的双重障碍。富含电子的烯酮缩醛和烯胺都会被氧化，生成的自由基阳离子会被烯丙基硅烷亲核试剂捕获。后续反应的产物分析将与循环伏安法一起用于探索自由基阳离子中间体的性质以及如何操纵它们的后续反应。凭借这一奖项，有机和高分子化学计划支持华盛顿大学化学系的凯文·D·莫勒博士的研究。默勒教授和他的学生将探索利用电能来诱导有机分子的选择性反应。将开发电化学中介的反应序列，以允许有效地合成选定的有机分子。这种有机电化学反应为构建构成现代制药研究基础的复杂目标结构提供了简单但高度通用的工具。电化学方法也为有机合成提供了潜在的“绿色”(环境友好)方法。

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.