Organic Transformations via Activation of Monohalogenated Substrates in Copper Catalyzed Atom Transfer Radical Addition

有了这个奖项，化学部的化学催化项目资助迪克讷大学的Tomislav Pintauer博士开发新方法，以环保的方式生产药品和其他有用的化学品。新方法使用由铜形成的催化剂，而不是更常用的含有汞或其他有毒金属的催化剂。他们的工作有助于扩大这些铜催化剂可以使用的条件范围，以便可以使用不产生自由基的环境友好剂，如维生素C。他们的新方法很有吸引力，因为需要非常低浓度的金属，进一步减少了环境足迹，同时仍然为社会提供有用的化学品，如药物。通过在迪克讷大学开设关于绿色催化和其他主题的新课程，这项工作正在产生更广泛的影响。该研究小组正在进一步扩大他们的工作的影响，包括和指导代表性不足的少数民族和经济困难的高中学生从匹兹堡地区在他们的研究计划。这项研究的重点是开发高活性铜催化剂的原子转移自由基加成（ATRA）反应涉及一卤代底物，以及环化（ATRC）反应，导致形成合成有用的内酯。这两种方法都显示出利用各种烷基卤化物和烯烃介导C-C键形成的巨大潜力。目前，还没有已知的催化剂具有可接受的活性水平，因此这项工作填补了一个重要的空白。该项目的主要重点是专门定制的配体设计，特别强调铜配合物催化的碳卤键活化的结构和机理理解。

With this award, the Chemical Catalysis Program in the Chemistry Division is funding Dr. Tomislav Pintauer from Duquesne University to develop new methods to produce pharmaceuticals and other useful chemicals in an environmentally sound fashion. The new methods use catalysts formed from copper instead of the more commonly-used ones that contain mercury or other toxic metals. Their work is helping to expand the range of conditions where these copper catalysts can be used so that environmentally benign agents that do not generate free radicals, such as Vitamin C, can be used. Their new method is appealing because very low concentrations of metal are required, further reducing the environmental footprint while still providing society with useful chemicals such as drugs. The work is having a broader impact through the development of new courses at Duquesne University on green catalysis and other topics. The research team is further broadening the impact of their work by including and mentoring under-represented minority and economically disadvantaged high school students from the Pittsburgh area in their research program.This research is focused on developing highly active copper catalysts for atom transfer radical addition (ATRA) reactions involving monohalogenated substrates, as well as cyclization (ATRC) reactions leading to the formation of synthetically useful lactones. Both of these methods have shown great potential for mediating C-C bond formation utilizing a variety of alkyl halides and alkenes. Currently, there is no known catalyst with an acceptable level of activity for both of these transformations, so the work is filling an important void. The main focus of the project is specifically tailored ligand design, with special emphasis on structural and mechanistic understanding of the carbon-halogen bond activation catalyzed by copper complexes.