Palladium-Catalyzed Alkylation of Unactivated Olefins

钯催化未活化烯烃的烷基化

• 批准号: 0304994
• 负责人: Ross Widenhoefer
• 金额: $ 36万
• 依托单位: Duke University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2003
• 资助国家: 美国
• 起止时间: 2003-03-01 至 2006-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0304994&HistoricalAwards=false
• 关键词: Palladium; Catalyzed; Alkylation; Unactivated; Olefins

The foci of this research involve the palladium-catalyzed hydroalkylation and oxidative alkylation of unactivated olefins. The scope of hydroalkylation will be explored and the use of dialky ketones and electron-rich aryl groups will be used to develop processes for the formation of cyclopentanones, carbobicyclic and heterocyclic compounds. Intermolecular hydroalkylation processes will also be tested and the mechanism of palladium-catalyzed hydroalkylation wil be elucidated. Procedures for catalytic, asymmetric hdroalkylation will be developed as will tandem hydroalkylation/carbonylation and hydralkylation/carbometallation methodology. The scope of oxidative alkylation with respect to carbon nucleophiles and substitution will be examined and oxidative alkylation procedures terminated by beta-heteroatom elimination will be developed.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Ross A. Widenhoefer of the Department of Chemistry at Duke University. Professor Widenhoefer will focus his work on the development of methodologies for palladium-catalyzed alkylation of unactivated olefins. The chemistry holds great potential as a new method for C-C bond formation and could have an important broader impact on organic synthesis, in particular on the ability of synthetic chemists to construct complex naturally occurring and biologically active molecules of interest to the pharmaceutical industry. Aside from providing an excellent environment for the training of graduate students, the project will also involve participation of underrepresented minority undergraduate students from North Carolina Central University, a neighboring HBCU.

本研究的重点涉及未活化烯烃的钯催化加氢烷基化和氧化烷基化。 将探索加氢烷基化的范围，并使用二烷基酮和富电子芳基来开发形成环戊酮、碳双环和杂环化合物的方法。 还将测试分子间加氢烷基化过程，并阐明钯催化加氢烷基化的机理。 将开发催化、不对称加氢烷基化程序以及串联加氢烷基化/羰基化和加氢烷基化/碳金属化方法。将检查碳亲核试剂和取代的氧化烷基化范围，并开发通过β-杂原子消除终止的氧化烷基化程序。有机和高分子化学计划通过该奖项支持 Ross A. Widenhoefer 博士的研究杜克大学化学系教授。 Widenhoefer 教授的工作重点是开发未活化烯烃的钯催化烷基化方法。 该化学作为一种形成 C-C 键的新方法具有巨大的潜力，并且可能对有机合成产生更广泛的重要影响，特别是对合成化学家构建制药工业感兴趣的复杂天然存在和生物活性分子的能力。 除了为研究生的培训提供良好的环境外，该项目还将吸引来自邻近的 HBCU 北卡罗莱纳中央大学的少数族裔本科生参与。