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

SusChEM - 通过有氧碳氢键功能化反应进行可持续有机合成

• 批准号: 1362396
• 负责人: Paul Floreancig
• 金额: $ 45万
• 依托单位: University of Pittsburgh
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-09-01 至 2019-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1362396&HistoricalAwards=false
• 关键词: SusChEM; Sustainable; Organic; Synthesis; Through

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.

在这个由化学系化学合成项目资助的项目中，匹兹堡大学的Paul Floreancig教授正在开发有机合成中氧化键形成反应的环境友好方法。这一进展是通过使用廉价、无毒的化学计量氧化剂来再生醌类化合物，以及通过新的转化来显著缩短生物活性分子及其类似物的合成来实现的。这些努力提供了新的途径，通过碳-氢键功能化的方式，最大限度地减少废物的产生，以获得复杂的结构。教授Floreancig是前往学院和大学，有来自传统上在STEM领域代表性不足的群体的学生人数高，给研讨会，并让这些学生在有关科学职业的讨论。此外，Florencig博士将利用该奖项下开展的研究成果作为绿色氧化化学讲座的基础。该项目的重点是将通过氧化剂2，3-二氯-5，6-二氰基-1，4-苯醌（DDQ）的碳氢键断裂获得稳定碳阳离子的特殊能力与可见光介导的光氧化的环境效益相结合。DDQ通常以化学计量的量使用，并产生大量的还原产物废物。可见光介导的氧化采用环境友好的化学计量氧化剂，但在氧化阳离子形成方面没有显示出广泛的范围。使用可见光介导的氧化从还原产物再生DDQ提供了一种在减少废物形成的同时保持反应性的途径。研究几种催化剂体系可以确定这种新策略的理想催化剂结构。