Development and Applications of Aerobic Electron Transfer Initiated Cyclization Reactions

有氧电子转移引发环化反应的进展及应用

• 批准号: 0139851
• 负责人: Paul Floreancig
• 金额: $ 31.05万
• 依托单位: University of Pittsburgh
• 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: 2002-04-15 至 2005-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0139851&HistoricalAwards=false
• 关键词: Development; Applications; Aerobic; Electron; Transfer

With the support of the Organic Dynamics Program in the Chemistry Division, Professor Paul Floreancig, of the Department of Chemistry at the University of Pittsburgh, has begun a program in which electron transfer initiated carbon-carbon sigma-bond activation serves to trigger new synthetic transformations. Homobenzylic ethers and amides are used as the starting materials for electron transfer initiated cyclization (ETIC) reactions. In these reactions, photoinitiated single electron oxidation of the substrates form radical cation intermediates that undergo a facile displacement of a benzyl radical by pendent nucleophiles. The ultimate objective of the projects described in the proposal is to advance the ETIC method to a sufficient extent that it can serve as a method for efficient syntheses of complex natural projects and other medicinally and structurally important compounds.Professor Paul Floreancig, of the Department of Chemistry at the University of Pittsburgh, with the support of the Organic Dynamics Program, will establish new synthetic methodology and plans to develop applications of the chemistry, which minimizes impact to the environment and uses ETIC in the synthesis of acylaminals. This substrate will allow increased understanding of the structurally intriguing anticancer agent, pederin, which is isolated from South Pacific sponges.

在化学系有机动力学项目的支持下，匹兹堡大学化学系的 Paul Floreancig 教授启动了一项项目，其中电子转移引发的碳-碳西格玛键活化可触发新的合成转化。同苯甲基醚和酰胺用作电子转移引发环化（ETIC）反应的起始材料。在这些反应中，底物的光引发单电子氧化形成自由基阳离子中间体，该中间体容易被悬挂的亲核试剂取代苯甲基自由基。提案中描述的项目的最终目标是将 ETIC 方法推进到足够的程度，使其可以作为有效合成复杂天然项目和其他医学上和结构上重要的化合物的方法。匹兹堡大学化学系的 Paul Floreancig 教授在有机动力学计划的支持下，将建立新的合成方法并计划开发化学应用，从而最大限度地减少对化学的影响 环境并使用 ETIC 合成酰基胺。这种底物将有助于加深对结构上有趣的抗癌剂佩德林（pederin）的了解，佩德林是从南太平洋海绵中分离出来的。