Preparative Electron Transfer Photochemistry

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The emphasis of this work is on the development of new single electron transfer initiated photochemical reactions. Photochemical group transfer reactions which result from the formation of reactive dipolar intermediates will be investigated in detail. Photochemical preparation and trapping of 1,3 dipoles such as azomethine and carbonyl ylides will be studied as will 1,4 dipole forming and trapping reactions of alpha ketoamides and alpha ketoesters. Single electron transfer initiated photomacrocyclization reactions will also be studied, first using phthalimides. Photomacrocyclization of phthalimides will be used to determine the factors which govern efficiencies and regioselectivities of photocyclizations then that information will be applied to macrocyclic polyether, polyamide and polypeptide syntheses. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Patrick S. Mariano of the Department of Chemistry at the University of New Mexico. Dr. Mariano will explore photochemical group transfer, cyclization and redox reactions. The photocyclization reactions studied will serve as the foundation for new polyether, polyamide, and polypeptide syntheses and thus have potential applications for the preparation of antibiotics and other pharmaceuticals. Discovery of selective, photochemical amine oxidation reactions has potential applications in the design of inactivators of flavoenzymes such as monoamine oxidase. Students trained during the course of this work will be broadly trained in preparative organic chemistry and preparative photochemistry and gain skills needed by the pharmaceutical industry.