SusChEM: Copper Catalyzed C-H Functionalization

美国国家科学基金会化学催化计划支持蒂莫西·H. Warren教授设计和开发了碳-氮（C-N）、碳-氧（C-O）和碳-碳（C-C）键形成的新方案。这项研究是通过详细了解关键的碳-氢（C-H）活化和C-官能团（C-FG）键形成反应来推动的，以激发新的催化剂结构，实现可调的选择性。该团队开发了与未活化胺的C-H胺化反应，与醇和受保护酚的C-H醚化，与硝基烷烃的C-H硝基烷基化，与酮的C-H烷基化以及通过其他H-FG底物形成C-FG的反应。他们综合和机械地检查关键的铜（II）-FG中间体，以了解它们在C-FG键形成和H原子提取反应中的作用。 这些化学家研究了新的配体变体，以提高特别反应性铜（II）-FG中间体的寿命，并指导C-FG键形成步骤。各种各样的具有合成价值的、机械相关的C-H官能化反应解决了可持续化学合成中的重要挑战，例如使用氨将烃转化为胺。这项研究福尔斯“SusChEM”倡议，因为它促进了非贵金属催化剂-铜-的使用，而不是更稀有和昂贵的替代品。 与默克公司的合作使乔治敦大学的学生能够访问位于新泽西州拉威的默克催化和自动化实验室。 在默克实验室，学生们采用高通量方法来发现新的C-H官能化催化剂和催化转化。与Karsten Meyer教授（U.埃尔兰根，德国）和汤姆Cundari教授（美国）。北德克萨斯州）分别实现了深入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的低收入家庭的高风险中学生联系，在化学展上为他们的中学生提供有趣的科学节目（90-100名学生）在乔治敦举行，每年夏天以及至少一个较小的访问美国国家科学基金会的化学催化项目支持蒂莫西·H·史密斯教授的努力。Warren教授设计和开发了碳-氮（C-N）、碳-氧（C-O）和碳-碳（C-C）键形成的新方案。 这项工作解决了有价值的和可持续的化学合成，如使用氨将烃转化为胺。开发与碳形成键的新方法，消除对特定底物和保护/脱保护步骤的需要，可以加速有机化学合成并提高工业产量-同时减少环境足迹并提高化学合成的可持续性。虽然许多C-H官能化系统使用钯和其他贵金属，但这种方法使用铜-一种低成本和低毒性的地球上丰富的金属。 工业合作使研究生能够探索高通量的方法来发现，同时增加自己的就业市场。 在美国和德国正在进行的合作也为学生提供了在全球社区进行研究的更广阔的视角，提高了他们的技术和团队合作能力。 沃伦教授和他的团队与来自低收入家庭的高风险中学生在资源不足的社区连接，通过每年夏天的化学展提供科学编程，以及在哥伦比亚哥伦比亚特区公立学校关闭时偶尔对乔治敦大学进行较小的访问。

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.