Photooxygenations in Heterogeneous media

这项研究的重点是利用两种方法将氧气光化学引入沸石中的有机基质中。在第一种方法中，紫精电子转移增敏剂将用于激活不饱和底物，使其与三重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，我们将研究几种不同还原电位的紫精。此外，还将使用新型紫精阿托品来确定对映体选择性光氧化的可行性。在第二种方法中，将使用单线态氧增敏剂与烯烃和硫化物底物进行分子筛内单线态氧反应。将开发新的机械工具，如氧示踪剂和捕获实验，以了解这些沸石内的单线态氧反应。有了这个续展奖，有机和高分子化学计划正在支持怀俄明大学拉勒米分校化学系的爱德华·克伦南的研究和教育努力。克伦南教授将把研究重点放在开发将氧气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非常有兴趣。化学专业的研究生和博士后将在克伦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.