SusChEM: Copper Catalyzed C-H Functionalization

SusChEM：铜催化的 C-H 官能化

• 批准号: 1300774
• 负责人: Timothy Warren
• 金额: $ 44.3万
• 依托单位: Georgetown University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-09-01 至 2017-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1300774&HistoricalAwards=false
• 关键词: SusChEM; Copper; Catalyzed; Functionalization

The NSF Chemical Catalysis Program supports the efforts of Professor Timothy H. Warren of Georgetown University in the design and development of new protocols for carbon-nitrogen (C-N), carbon-oxygen (C-O), and carbon-carbon (C-C) bond formation. This research is propelled by a detailed understanding of the key carbon-hydrogen (C-H) activation and C-functional group (C-FG) bond forming reactions to motivate new catalyst architectures for tunable selectivity. The team develops C-H amination reactions with unactivated amines, C-H etherification with alcohols and protected phenols, C-H nitroalkylation with nitroalkanes, and C-H alkylation with ketones as well as C-FG forming reactions via other H-FG substrates. They synthetically and mechanistically examine key copper(II)-FG intermediates to understand their roles in C-FG bond formation and H-atom abstraction reactions. These chemists examine new ligand variations to enhance the lifetime of particularly reactive copper(II)-FG intermediates as well as to direct the C-FG bond forming step. A wide range of synthetically valuable, mechanistically related C-H functionalization reactions address important challenges in sustainable chemical synthesis, such as the conversion of hydrocarbons to amines using ammonia. This research falls under the "SusChEM" initiative as it promotes the use of non-precious metal catalysts - copper - over more rare and expensive alternatives. Collaboration with Merck allows Georgetown students to access the Merck Catalysis and Automation Laboratory in Rahway, NJ. At the Merck laboratories, the students employ high throughput approaches to the discovery of new C-H functionalization catalysts and catalytic transformations. Ongoing collaborations with Prof. Karsten Meyer (U. Erlangen, Germany) and with Prof. Tom Cundari (U. North Texas) enable in depth spectroscopic studies and computational insights, respectively. Through the organization "Higher Achievement", Professor Warren connects with high-risk middle school students from low income families in under-resourced communities, providing fun science programming to their middle school scholars in a Chemistry Show (90-100 students) held at Georgetown each summer as well as at least one smaller visit (10-20 students) to Georgetown during each academic year when DC public schools are closed.The NSF Chemical Catalysis Program supports the efforts of Professor Timothy H. Warren of Georgetown University in the design and development of new protocols for carbon-nitrogen (C-N), carbon-oxygen (C-O), and carbon-carbon (C-C) bond formation. This work addresses valuable and sustainable chemical synthesis, such as the conversion of hydrocarbons to amines using ammonia. The development of new methodologies for bond formation with carbon that eliminate the need for specific substrates and protection / deprotection steps can accelerate organic chemical synthesis as well as enhance industrial throughput - all while reducing the environmental footprint and enhancing the sustainability of chemical synthesis. While many C-H functionalization systems employ palladium and other noble metals, this approach employs copper - an Earth-abundant metal of low cost and toxicity. Industrial collaborations allow graduate students to explore high throughput approaches to discovery while increasing their own job marketability. Ongoing collaborations within the U.S. and in Germany also provide students with the broader perspective of performing research in a global community, enhancing both their technical and teamwork skills. Professor Warren and his group connect with high-risk middle school students from low income families in under-resourced communities, providing science programming via a Chemistry Show each summer as well as during occasional smaller visits to Georgetown Univeristy held when District of Columbia public schools are closed.

NSF化学催化计划支持乔治敦大学的Timothy H. Warren教授在设计和开发碳氮（C-N），碳氧气（C-O）和碳碳（C-C）债券的新方案。这项研究是通过对关键的碳氢（C-H）激活和C功能组（C-FG）键形成反应的详细了解来推动这项研究的，以激发新的催化剂体系结构以实现可调性选择性。该团队通过未活化的胺，与醇和受保护的苯酚，C-H硝基烷基化一起使用C-H胺化反应，用硝基烷烃和酮的C-H烷基化以及C-H烷基化以及通过其他H-FG底物形成C-FG反应。它们合成和机械学检查关键铜（II）-FG中间体，以了解其在C-FG键形成和H原子抽象反应中的作用。 这些化学家检查了新的配体变化，以增强特别反应性铜（II）-FG中间体的寿命以及指导C-FG键形成步骤。多种合成有价值的机械性，机械性相关的C-H功能化反应解决了可持续化学合成的重要挑战，例如使用氨的碳氢化合物转化为胺。这项研究属于“ Suschem”倡议，因为它促进了非贵金属催化剂的使用 - 铜 - 而不是稀有和昂贵的替代品。 与默克公司的合作使乔治敦的学生可以访问新泽西州拉威的默克催化和自动化实验室。 在默克实验室，学生采用高通量方法来发现新的C-H功能化催化剂和催化转化。与Karsten Meyer教授（德国U. Erlangen）和汤姆·康达里（Tom Cundari）教授（美国北德克萨斯州）进行了持续的合作，分别启用了深度的光谱研究和计算见解。通过组织“更高的成就”，沃伦教授与来自资源不足社区低收入家庭的高风险中学学生联系，为每年夏天在乔治敦举行的化学表演（90-100名学生）的中学学者提供有趣的科学节目乔治敦大学的蒂莫西·H·沃伦（Timothy H. 这项工作解决了有价值且可持续的化学合成，例如使用氨将碳氢化合物转化为胺。用碳形成新的方法论，消除了对特定底物的需求和保护 /脱保护步骤，可以加速有机化学化学合成，并增强工业吞吐量 - 同时降低了环境足迹并增强了化学合成的可持续性。尽管许多C-H功能化系统采用钯和其他贵族金属，但这种方法采用铜 - 一种低成本和毒性的土壤。 工业合作使研究生能够探索高通量的发现方法，同时提高自己的工作可销售性。 美国和德国的持续合作还为学生提供了在全球社区进行研究的更广泛的观点，从而提高了他们的技术和团队合作能力。 沃伦（Warren）教授及其小组与来自资源不足社区的低收入家庭的高风险中学生联系，每年夏天通过化学节目以及偶尔访问哥伦比亚大学公立学校时举行的乔治敦大学（Georgetown Univeristy）的较小访问。