Catalytic C-H Amination with Late Metal Nitrenes and Amides

在这个由化学系化学催化计划资助的项目中，乔治城大学的Timothy H.Warren教授将开发催化碳-氢(C-H)胺化反应，作为一种不需要预先对反应中心进行官能化的方法来制备新的碳-氮(C-N)键。直接影响C-H到C-N转化的能力，而不需要分离、纯化和转化相应的前体，提供了降低成本、能源消耗和环境影响的诱人前景。在先前结果的基础上，该方法将铜和镍的硝胺络合物的化学和电子结构与它们的催化反应活性联系起来。这项工作具体考察了来自有机叠氮化合物的铜和镍的氮化物络合物，反应的胺和底物范围，以及进一步提高催化反应效率和范围的新催化剂结构。这个项目的更广泛的影响包括国家和国际合作，这将扩大学生在更大的科学界内进行科学的视角。沃伦教授积极指导高中生、本科生(特别是通过NSF赞助的REU计划)和研究生。这项工作将扩大可用于含C-N键化合物的化学合成的方法库。这些研究的结果可能会对合成和材料化学中的各种应用产生许多重要的长期影响，特别是在医药或医药产品中。

In this project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Timothy H. Warren of Georgetown University will develop catalytic carbon-hydrogen (C-H) amination reactions as a means of preparing new carbon-nitrogen (C-N) bonds without the need to pre-functionalize the reactive sites. The ability to directly affect the C-H to C-N transformation without the need to isolate, purify, and transform corresponding precursors offers the appealing prospect of reduced cost, energy consumption and environmental impact. Building on previous results, this approach connects the chemical and electronic structures of copper and nickel nitrene and amide complexes to their catalytic reactivity. The work specifically examines copper and nickel nitrene complexes derived from organoazides, the amine and substrate scope of the reactions, and new catalysts architectures to further enhance the efficiency and scope of the catalytic reactions. The broader impacts of this project include national and international collaborations that will expand the student's perspective on the way science is conducted within the larger scientific community. Professor Warren is active in mentoring high school students, undergraduates (especially through the NSF-sponsored REU program) and graduate students.This work will expand the repertoire of methods that can be used in the chemical synthesis of compounds containing C-N bonds. The results of these studies could have many important long term impacts on a variety of applications in synthetic and materials chemistry, particularly in medicinal or pharmaceutical products.