Photochemistry of Sulfoxides and Analogs: The Hunt for Oxene, Nitrenes, and Carbenes

该提案描述了实验工作，涉及光化学引发的脱氧，α-裂解和立体突变的亚砜，以及潜在的光生氮烯和卡宾从sulfilimines和锍叶立德。 与加州大学洛杉矶分校的Miguel Garcia-Garibay的合作将用于研究光诱导氧原子转移实验中重原子隧穿的可能参与。 亚砜的辐照产生极活泼的氧化剂，詹克斯小组将确定这些氧化是通过氧原子转移发生的，还是通过氧原子的产生，然后与被氧化的分子反应发生的。 硫亚胺和锍叶立德的类似辐照也应该为有机化学家提供其他活性中间体，如氮烯和卡宾。 有了这个奖项，有机和高分子化学计划是支持威廉博士的研究。爱荷华州州立大学化学系的詹克斯说。 詹克斯博士和他的合作者将致力于了解光化学引发的氧化反应和其他产生活性中间体的光化学反应的机制。 氧化反应是自然界中最普遍的反应之一，氧原子转移反应广泛存在于植物和动物中，并用于合成特种化学品。 从事该项目的研究生将获得合成和理论有机化学方面的跨学科培训，这两者都是制药和特种化学品行业所需的技能。

This proposal describes experimental work involving photochemically initiated deoxygenation, alpha-cleavage and stereomutation of sulfoxides as well as the potential photogeneration of nitrenes and carbenes from sulfilimines and sulfonium ylides. A collaboration with Miguel Garcia-Garibay at UCLA will be used to investigate the possible involvement of heavy atom tunneling in the photoinduced oxygen atom transfer experiments. Irradiation of sulfoxides generates extremely reactive oxidizing agents and the Jenks group will be determining whether these oxidations occur by oxygen atom transfer or generation of oxygen atoms followed by their reaction with the molecules which are oxidized. Similar irradiations of sufilimines and sulfonium ylides should also provide organic chemists with access to other reactive intermediates such as nitrenes and carbenes. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. William S. Jenks of the Department of Chemistry at Iowa State University. Dr. Jenks and his collaborator will work on understanding the mechanisms of photochemically initiated oxidation reactions and other photochemical reactions which generate reactive intermediates. Oxidation reactions are some of the most ubiquitous reactions in nature and oxygen atom transfer reactions occur widely in plants and animals and are used in the synthesis of speciality chemicals. Research students who work on this project will gain interdisciplinary training in aspects of synthesis and theoretical organic chemistry, both of which are skills needed by the pharmaceutical and speciality chemicals industries.