This grant in the Organic and Macromolecular Chemistry Program supports research by Dr. Ned Porter aimed at explaining features of the mechanisms of chemical reactions which involve free radicals as reaction intermediates. Such reactions are quite common in organic chemistry and in the chemistry of life processes, such as lipid oxidation, tissue damage, and aging. The three areas of research covered in this grant are: (a) free radical hydroperoxide rearrangements; (b) examination of the hydrophobic effect as a potential perturbation of chemical reactivity and stereochemistry; and (c) the study of factors involved in free radical macrocyclization and transannular cyclization. The reaction of fats and oils with molecular oxygen, a free radical reaction that generates hydroperoxides, has been implicated in the aging process. Dr. Porter's research involves fundamental studies of the chemical processes involved in the reaction of organic molecules with molecular oxygen. Free radicals are also being used extensively in organic synthesis and the Porter group has discovered a new method for construction of large-ring molecules using free radicals. This work will explore the limitations and possibilities of this new reaction. Finally, the effect of water on the chemical reactivity and stereochemistry of organic molecules that have mixed solutions such as soaps will be investigated. Early evidence indicates that molecular aggregates formed from soap-like molecules in water can exert dramatic and unusual stereochemical effects on these molecules.
