Intramolecular Anodic Olefin Coupling Reactions

分子内阳极烯烃偶联反应

• 批准号: 0514087
• 负责人: Kevin Moeller
• 金额: $ 37.8万
• 依托单位: Washington University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-08-01 至 2008-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0514087&HistoricalAwards=false
• 关键词: Intramolecular; Anodic; Olefin; Coupling; Reactions

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.

这个更新项目以电化学介导的氧化环化反应为中心。天然产物arteanuinn B和arteanuin M的合成将用于探索构建alliacol A的合成策略的通用性，artemisolide的合成将用于探索“Curtin-Hammett控制”环化的合成效用，ineleganolide的合成将用于研究烯二醇引发基环化的效用。而丹卡酮的合成将用于确定与引发烯烃上的吸电子基团的阳极环化的相容性。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，使它们有利于碳-碳键的形成，以克服六元环和四元碳形成的双重障碍。富电子的烯酮缩醛和烯胺都将被氧化，产生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与循环伏安法一起使用，以探测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。有了这个奖项，有机和大分子化学项目支持华盛顿大学化学系凯文·d·莫勒博士的研究。莫勒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，允许有效的合成选定的有机分子。这种有机电化学反应为构建复杂的目标结构提供了简单而又高度通用的工具，这些结构构成了现代药物研究的基础。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。