This research focuses on the free radical oxidation of organic compounds. Isotopically-labelled hydroperoxides will be used to detail the mechanism of the radical oxidations of biologically relevant media such as micelles, lipid bilayers and lipoproteins. Chiral metal complexes capable of acting as Lewis acids will be bound to appropriately functionalized alkenes and used in a novel manner to impose enantioselectivity on the radical reactions. Lastly, new free radical copolymerization procedures will be examined as a route to stoichiometrically well-defined alternating copolymers. Graduate and postdoctoral students will be introduced to the synthesis and characterization of isotopically-labelled compounds, and the use of these and other specifically designed reagents as mechanistic probes of the reactions. With this award, the Organic and Macromolecular Chemistry Program supports the research and educational activities of Dr. Ned Porter of Duke University. Professor Porter will focus his research on garnering fundamental information on free-radical oxidations. Although known for some time, recognition of the role of organic free radicals in different biochemical processes, as well as their increasing applications in organic and material syntheses creates the need to elucidate the chemistry of these reactive intermediates. This research utilizes unique isotopically-labelled molecules to probe the mechanisms of free radical oxidations of organic substrates, and novel organometallic adducts to examine an innovative approach to imposing stereochemical control on the reactions. Professor Porter's educational activities involve the training of graduate and postdoctoral students. u¬
