SusChEM: Mechanistic Investigations of Oxidative Carbon-Hydrogen Functionalization Reactions

SusChEM：氧化碳氢功能化反应的机理研究

• 批准号: 1566392
• 负责人: Brenton DeBoef
• 金额: $ 36万
• 依托单位: University of Rhode Island
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-09-01 至 2020-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1566392&HistoricalAwards=false
• 关键词: SusChEM; Mechanistic; Investigations; Oxidative; Carbon

The Chemical Synthesis Program of the Chemistry Division supports the project by Professor Brenton DeBoef of the University of Rhode Island. Professor DeBoef is developing new chemical reactions that convert carbon-hydrogen bonds to carbon-nitrogen or carbon-carbon bonds. These reactions are significant because most organic molecules are constructed with a skeletal framework containing carbon-carbon and carbon-nitrogen bonds, surrounded by many carbon-hydrogen bonds on their periphery. Consequently, the ability to directly convert selected carbon-hydrogen bonds to other bonds is a valuable tool for chemists. The key to the development of these new reactions is the use of new gold and iron-based catalysts. These new reactions will help chemists construct technologically relevant, complex molecules such as pharmaceuticals, conducting polymers and organic dyes. Additionally, Professor DeBoef has formed a joint research and training program with the Community College of Rhode Island in which students in the Chemical Technology program synthesize a potential Alzheimer's drug. This collaboration is having an impact by expanding research infrastructure and scientific workforce training. The overarching objective of the project is to systematically test mechanistic hypotheses concerning the catalytic synthesis of carbon-carbon (C-C) and carbon-nitrogen (C-N) bonds via oxidative carbon-hydrogen (C-H) bond activation. Accomplishing these goals provides fundamental knowledge about the mechanistic steps by which noble or earth-abundant transition metal catalysts cleave strong, non-acidic C-H bonds. Specifically, this proposal seeks to discover the active catalytic species in a gold catalyzed regioselective C-H amination reaction and an iron-catalyzed C-H arylation reaction. DeBoef has hypothesized that the former reaction is catalyzed by a unique dimeric gold species. An iron catalyst, whose resting state is in the unique +1 oxidation state, is hypothesized to catalyze the latter reaction. The fundamental knowledge gained by this work facilitates the development of novel chemical reactions and synthetic schemes. The DeBoef group contributes to the training of a diverse workforce in science by providing an excellent training environment for both graduate and undergraduate students, including women and minorities. Additionally, the outreach work with the Community College of Rhode Island provides aspiring chemical technicians with a meaningful and marketable research experience.

化学系的化学合成项目支持罗得岛大学的Brenton DeBoef教授的项目。DeBoef教授正在开发新的化学反应，将碳-氢键转化为碳-氮或碳-碳键。这些反应是重要的，因为大多数有机分子都是由含有碳-碳和碳-氮键的骨架构成的，在它们的外围被许多碳氢键包围。因此，直接将选定的碳-氢键转化为其他键的能力对化学家来说是一个有价值的工具。开发这些新反应的关键是使用新的金基和铁基催化剂。这些新的反应将帮助化学家构建技术相关的复杂分子，如药物，导电聚合物和有机染料。此外，DeBoef教授还与罗得岛社区学院建立了一个联合研究和培训项目，在该项目中，化学技术项目的学生合成了一种潜在的阿尔茨海默病药物。这种合作通过扩大研究基础设施和科学劳动力培训产生了影响。该项目的总体目标是系统地测试关于通过氧化碳氢（C-H）键活化催化合成碳-碳（C-C）和碳-氮（C-N）键的机理假设。实现这些目标提供了关于贵金属或富含地球的过渡金属催化剂裂解强非酸性C-H键的机械步骤的基础知识。具体而言，该提议旨在发现金催化的区域选择性C-H胺化反应和铁催化的C-H芳基化反应中的活性催化物种。DeBoef假设前一个反应是由一种独特的二聚金物种催化的。铁催化剂，其静止状态是在独特的+1氧化态，被假设催化后者的反应。这项工作获得的基础知识促进了新的化学反应和合成方案的发展。DeBoef集团通过为研究生和本科生（包括妇女和少数民族）提供良好的培训环境，为科学领域的多元化劳动力培训做出了贡献。此外，与罗得岛社区学院的外联工作为有抱负的化学技术人员提供了有意义和有市场的研究经验。