Photooxygenations in Heterogeneous media

本研究的重点是利用两种方法将氧光化学引入沸石中的有机底物。在第一种方法中，将使用紫外光电子转移敏化剂来激活不饱和底物，使其与三态氧或超氧化物发生反应。为了了解影响活性和反应效率的因素，我们将研究几种具有不同还原电位的病原菌。此外，使用新的暴力分子的atropisomer将被用来确定对映选择性光氧化的可行性。在第二种方法中，单线态氧敏化剂将用于与烯烃和硫化物底物进行沸石内单线态氧反应。新的机理工具，如氧示踪和捕获实验将发展，以了解这些沸石内单线态氧反应。有了这个更新奖，有机和大分子化学项目正在支持怀俄明州拉勒米大学化学系的爱德华·克莱南的研究和教育工作。克莱南教授的研究将集中在开发将氧引入碳氢化合物的新方法上，这对农业、制药和精细化工行业都有很大的兴趣。研究生和博士后水平的化学学生将在克莱南教授的实验室接受培训。

The focus of this research is in the photochemical introduction of oxygen into organic substrates in zeolites using two approaches. In the first approach a viologen electron-transfer sensitizer will be used to activate unsaturated substrates towards reaction with either triplet oxygen or superoxide. Several viologens with different reduction potentials will be studied in order to understand the factors that influence the viability and reaction efficiencies. In addition, the use of novel atropisomers of viologens will be used to determine the feasibility of enantioselective photooxygenations. In the second approach singlet oxygen sensitizers will be used to conduct intrazeolitic singlet oxygen reactions with both alkene and sulfide substrates. New mechanistic tools such as oxygen tracer and trapping experiments will be developed in order to understand these intrazeolite singlet oxygen reactions.With this renewal award, the Organic and Macromolecular Chemistry Program is supporting the research and educational efforts of Edward Clennan of the Department of Chemistry at the University of Wyoming, Laramie. Professor Clennan will focus his research on the development of new ways to introduce oxygen into hydrocarbons, which is of great interest to the agricultural, pharmaceutical and fine chemicals industries. Chemistry students at the graduate and post-doctoral level will be trained in Professor Clennan's lab.