Previous work on this project has demonstrated the self-oligomerization of trifluoromethylcopper to form CF3(CF2)nCu(n=1 to 16). The use of ?CF3Cu! as a ?CF2! transfer agent with other perfluorinated organometallic reagents is planned, and the generality and mechanism of the ?CF2! insertion process will be investigated. Alternative sources of ?CF2! will be studied for use with less reactive organometallic compounds. A broad study of alpha-halogen effects in alpha-halo and alpha, alpha-dihaloperfluoro organometallic reagents and of the scope of cumulene formation will be done. Complementary to this approach is the synthesis and chemistry of perfluoro diene-ynes. As an adjunct of the organometallic and phosphorus chemistry, a long range study will be made of the preparation of perfluoro-polyenes and the study of unique chemistry of these relatively unknown systems. The development of cis- and trans-difluoroethylene synthons will be part of the synthetic methodology for F-polyenes. These will be utilized as new synthons for the stereospecific preparation of perfluorobutadiene derivatives. In the area of ylide chemistry, a practical approach to functionalized fluoroolefin derivatives via an intramolecular Wadsworth-Emmons reaction using ylide/acylation methodology developed earlier will be undertaken. Related work with alkylated fluorinated ylides is planned as a new and practical route to alpha-fluoromethylene ylides. Finally, the study of new single electron transfer (SET) reactions will provide new or improved routes to fluoromethylene and difluoromethyl functionalized derivatives of biological interest. With this award, the Organic Synthesis Program will support the research of Dr. Donald J. Burton at the University of Iowa. The studies will continue the development of new synthetic methodology for the introduction of fluorine into organic molecules and the development of the ofttimes unique chemistry that results. This may lead to new kinds of chemicals and materials that should benefit research in biochemistry and medicine, as well as in the chemical industry.
