An investigation of stereochemical control of free radical addition processes will be conducted. The overall goal of the research is to define the mechanism of free radical addition processes which results in exact control of the stereochemistry of the final products generated. Reactions to be investigated during the course of this project include radical additions, atom transfer, and polymerizations of alkenes bearing amide auxiliaries. Precise regulation of the tacticity of specifically engineered oligomers and polymers will be accomplished by use of very specific stereochemical reactions. The exact distribution of oligomers will be regulated by reactions in micellar environments designed to produce a discrete number of reaction steps. In addition, the chemistry of peroxyl radical rearrangement and cyclization reactions will be investigated by the use of stereochemical probes and oxygen isotopes. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor N. A. Porter at Duke University. The studies will center around efforts to engineer the exact structure of molecules by extremely efficient and selective free radical reactions. By forcing chemical reactions to take place in very specific pathways, it is possible to generate molecules that are designed to solve important problems by virtue of their carefully controlled structure. One of the final goals of this work is to make molecules which have many repeat units of exactly the same orientation in space. This will result in molecules with very unusual properties.