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.
