Intramolecular Anodic Olefin Coupling Reactions

分子内阳极烯烃偶联反应

• 批准号: 0210175
• 负责人: Kevin Moeller
• 金额: $ 36万
• 依托单位: Washington University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-07-01 至 2005-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0210175&HistoricalAwards=false
• 关键词: Intramolecular; Anodic; Olefin; Coupling; Reactions

With this award Professor Moeller will continue his work on the use of intramolecular anodic olefin coupling reactions in synthetic organic electrochemistry. This work involves the development of stereocontrolled synthetic methods based on radical cation chemistry and then the utilization of these chemical reactions in the synthesis of natural products. Proposed new method development on asymmetric electrochemical cyclizations utilizing chiral ketene acetals as substrates could lead to a new enantioselective carbon-carbon bond forming reaction. Reactions discovered with prior NSF support will be applied to several total syntheses in the new support period. The first two total syntheses involve key tandem cyclizations, the first of which are initiated by electrochemically generated enol ether radical cations, whereas the last two syntheses utilize highly functionalized furans as the initiating group. 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 in St. Louis. Dr. Moeller will work on the use of electrolysis to generate chemical species which react with predictable patterns and selectivities. Use of electrolysis to generate reactive intermediates may prove to be a new "green" synthetic method with potential industrial applications. If large quantities of oxidants and reductants currently used in organic synthesis could be replaced by reliable electrochemical methods then many redox synthetic methods could be made more environmentally friendly. This group will also explore stereoselective oxidative cyclization reactions. These reactions produce molecules which are chiral (have two nonsuperimposable mirror images) and make only one of the two possible forms (a single enantiomer). Development of this family of reactions is one of the most important problems facing the pharmaceutical industry today. When developed, Dr. Moeller's work could be applied to the environmentally friendly syntheses of a number of biologically active molecules. Students trained during the course of this work will gain skills needed by the pharmaceutical industry which now produces a number of single enantiomer compounds.

有了这个奖项，Moeller教授将继续他在合成有机电化学中使用分子内阳极烯烃偶联反应的工作。 这项工作涉及基于自由基阳离子化学的立体控制合成方法的发展，然后利用这些化学反应合成天然产物。 以手性烯酮缩酮为底物的不对称电化学环化反应的新方法的发展，可能会导致一个新的对映选择性的碳-碳键形成反应。 在NSF先前的支持下发现的反应将在新的支持期内应用于几个全合成。 前两个总合成涉及关键的串联环化，其中第一个由电化学产生的烯醇醚自由基阳离子引发，而最后两个合成利用高度官能化的呋喃作为引发基团。 有了这个奖项，有机和高分子化学计划是支持博士凯文D。位于圣路易斯的华盛顿大学化学系的Moeller说。 Moeller博士将致力于使用电解来产生化学物质，这些化学物质以可预测的模式和选择性进行反应。 利用电解生成活性中间体可能被证明是一种新的“绿色”合成方法，具有潜在的工业应用。 如果目前在有机合成中使用的大量氧化剂和还原剂可以被可靠的电化学方法所取代，那么许多氧化还原合成方法可以变得更加环境友好。 这个小组也将探索立体选择性氧化环化反应。 这些反应产生的分子是手性的（有两个不可重叠的镜像），并且只产生两种可能形式之一（单一对映异构体）。 这类反应的发展是当今制药工业面临的最重要的问题之一。 Moeller博士的工作可以应用于许多生物活性分子的环境友好合成。 在这项工作的过程中培训的学生将获得制药行业所需的技能，现在生产一些单一的对映体化合物。