Palladium-Catalyzed Alkylation of Unactivated Olefins

本研究的重点是钯催化的未活化烯烃的氢烷基化和氧化烷基化反应。将探索氢烷基化的范围，并使用二烷酮和富含电子的芳基来开发形成环戊酮、碳双环和杂环化合物的方法。还将测试分子间氢烷基化过程，并阐明钯催化氢烷基化的机理。将制定催化不对称氢烷基化的程序以及串联的氢烷基化/羰基化和氢烷基化/碳金属化方法。将审查与碳亲核试剂和取代有关的氧化烷基化的范围，并将开发通过消除β-杂原子而终止的氧化烷基化程序。有了这个奖项，有机和高分子化学计划将支持杜克大学化学系的罗斯·A·威登霍夫博士的研究。Wdenhoefer教授将专注于开发钯催化的未活化烯烃的烷基化方法。化学作为一种新的C-C键形成方法具有巨大的潜力，并可能对有机合成产生重要的更广泛的影响，特别是对合成化学家构建制药工业感兴趣的复杂的自然存在的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，该项目还将让来自邻近的HBCU的北卡罗来纳中央大学的少数族裔本科生参与进来。

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.