Palladium-Catalyzed Alkylation of Unactivated Olefins

本研究的重点是钯催化未活化烯烃的加氢烷基化和氧化烷基化反应。 将探索加氢烷基化的范围，并将使用二烷基酮和富电子芳基来开发用于形成环戊酮、碳双环和杂环化合物的工艺。 分子间加氢烷基化过程也将被测试和钯催化加氢烷基化的机理将被阐明。 将开发催化、不对称加氢烷基化的程序，以及串联加氢烷基化/羰基化和加氢烷基化/卡波姆化方法。将对碳亲核试剂和取代的氧化烷基化范围进行检查，并将开发通过消除β-杂原子终止的氧化烷基化程序。他是杜克大学化学系的教授。 教授Wessenhoefer将集中他的工作在钯催化烷基化未活化的烯烃的方法的发展。 该化学作为C-C键形成的新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天然存在的生物活性分子的能力。 除了为研究生的培训提供一个良好的环境外，该项目还将涉及来自邻近HBCU的北卡罗来纳州中央大学的代表性不足的少数民族本科生的参与。

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.