Intramolecular Anodic Olefin Coupling Reactions

分子内阳极烯烃偶联反应

• 批准号: 9904336
• 负责人: Kevin Moeller
• 金额: $ 31.8万
• 依托单位: Washington University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1999
• 资助国家: 美国
• 起止时间: 1999-07-01 至 2002-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9904336&HistoricalAwards=false
• 关键词: Intramolecular; Anodic; Olefin; Coupling; Reactions

With this award, the Organic and Macromolecular Chemistry Program supports the research of Professor Kevin D. Moeller of Washington University. This research project studies intramolecular anodic olefin coupling reactions, in which carbon-carbon bond formation occurs to afford cyclic products which retain functional group handles for further synthetic elaboration. Professor Moeller is exploiting this reactivity for the synthesis of angularly-fused triquinanes and related 5-6-5-fused ring systems (alliacol A). Analogous olefin-heteroatom couplings offer access to pyrrolidine rings, leading to synthesis of the immunosuppressant FR901483. Through the oxidation of chiral enolate equivalents and subsequent nucleophilic trapping of the resulting radical cations, Professor Moeller seeks asymmetric coupling reactions, while other studies address the reversal of polarity in intermolecular alkylation reactions and the development of new oxidative routes to heterocycles.Formation of carbon-carbon bonds represents one of the most critical requirements for the synthesis of complex organic molecules, and Professor Moeller is developing new methods to accomplish this. In his method, the driving force for carbon-carbon bond formation is provided by the removal of electrons from selected reactants. Although such oxidation reactions are often effected by a variety of chemical oxidants, Professor Moeller exploits electrochemical techniques, using equipment as simple as a 6-Volt lantern battery to carry out the desired transformations.

有了这个奖项，有机和高分子化学计划支持教授凯文D。华盛顿大学的Moeller。 本研究计划主要研究分子内阳极烯烃偶联反应，其中碳-碳键的形成提供环状产物，这些环状产物保留了进一步合成的官能团。 Moeller教授正在利用这种反应性来合成角稠合的triquinanes和相关的5-6-5-稠环系统（alliacol A）。 类似的烯烃-杂原子偶联提供了进入吡咯烷环的途径，导致免疫抑制剂FR 901483的合成。 通过手性烯醇化物等价物的氧化和随后对所得自由基阳离子的亲核捕获，Moeller教授寻求不对称偶联反应，而其他研究则解决了分子间烷基化反应中极性的逆转以及杂环新氧化路线的开发。碳-碳键的形成是合成复杂有机分子的最关键要求之一，莫勒教授正在开发新的方法来实现这一点。 在他的方法中，碳-碳键形成的驱动力是通过从选定的反应物中移除电子来提供的。 虽然这种氧化反应通常受到各种化学氧化剂的影响，但Moeller教授利用电化学技术，使用像6伏灯笼电池一样简单的设备来进行所需的转化。