The development of new and synthetically useful reactions based upon cation radical catalysis is planned. The advantages and attributes of these new reactions will be investigated by means of thorough study of their selectivity profiles and mechanisms. Extremely sensitive mechanistic probes for the cation radical intermediates involved in catalyzed reactions have been designed and will be further quantitated and perfected. These probes will permit the definitive detection of these catalytic mechanisms, in general, where these are operative. The full scope of this powerful, new catalytic principle can thus be defined. The involvement of a catalytic mechanism in biological and enzyme model catalyzed epoxidation will be examined using these probes. The involvement of radical cation catalysis in, or its relationship to other biological oxidation reactions will also be examined. %%% With this award, the Organic Synthesis Program will continue to support the research of Dr. Nathan L. Bauld at the University of Texas. The research explores new ramifications and applications of the chemistry of cation radicals. It will generate new methodology that should benefit research in biochemistry and medicine as well as in the chemical industry.