SusChEM - Sustainable Organic Synthesis Through Aerobic Carbon-Hydrogen Bond Functionalization Reactions

在这个由化学系化学合成计划资助的项目中，匹兹堡大学的Paul Floreancig教授正在开发对环境无害的方法，用于有机合成中的氧化键形成反应。这一进展是通过使用廉价、无毒的化学计量比氧化剂来再生苯二酚，以及通过显著缩短生物活性分子及其类似物的合成的新转化来实现的。这些努力提供了通过碳氢键功能化以最大限度减少废物产生的方式获得复杂结构的新途径。弗洛雷西格教授正在前往学生人数众多的学院和大学，这些学生来自STEM领域传统上代表性较低的群体，他们将举办研讨会，并让这些学生参与关于科学职业的讨论。此外，弗洛伦西格博士将利用该奖项下进行的研究结果作为绿色氧化化学讲座的基础。该项目侧重于将氧化剂2，3-二氯-5，6-二氰基-1，4-苯二酚(DDQ)通过碳氢键断裂获得稳定的碳正离子的卓越能力与可见光介导的光氧化的环境效益相结合。滴滴涕通常以化学计量的数量使用，会产生大量的减少产品废物。可见光介导的氧化使用环境友好的化学计量比氧化剂，但在氧化阳离子的形成中没有显示出广泛的范围。利用可见光介导的氧化反应从还原产物中再生DDQ提供了一条在保持反应性的同时减少废物形成的途径。通过研究几种催化剂体系，可以确定这一新策略的理想催化剂结构。

In this project funded by the Chemical Synthesis program of the Chemistry Division, Professor Paul Floreancig of the University of Pittsburgh is developing environmentally benign approaches to oxidative bond forming reactions in organic synthesis. The advance is achieved through the use of inexpensive, non-toxic stoichiometric oxidants to regenerate quinones and through new transformations that significantly shorten the synthesis of biologically active molecules and their analogs. These efforts provide new routes to access complex structures through carbon-hydrogen bond functionalization in a manner that minimizes waste generation. Professor Floreancig is traveling to colleges and universities that have high populations of students from groups that are traditionally underrepresented in the STEM fields to give seminars and to engage these students in discussions about scientific careers. In addition, Dr. Florencig will use the results of the research carried out under this award as the basis for lectures on green oxidation chemistry. This project focuses on merging the exceptional capacity to access stabilized carbocations through carbon-hydrogen bond cleavage by the oxidant 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) with the environmental benefits of visible light-mediated photooxidation. DDQ is commonly used in stoichiometric quantities and generates significant quantities of reduction product waste. Visible light-mediated oxidations employ environmentally benign stoichiometric oxidants but do not show broad scope in oxidative cation formation. Using visible light-mediated oxidations to regenerate DDQ from the reduction product provides a path to retaining reactivity while reducing waste formation. Investigating several catalyst systems allow determination of the ideal catalyst structures for this new strategy.