The Organic Synthesis Program will provide support to Dr. Gary E. Keck of the Department of Chemistry at the University of Utah. This research will develop new synthetic methodology based on free radical reactions. The synthesis of the increasingly complex compounds used in modern agriculture and medicine will be aided by this work. The main focus of the work will center on the development of new conjunctive reagents for the preparation of cyclic compounds (particularly five- and six-membered rings) via radical chain processes, explorations of the free radical chemistry of vinyl oxiranes, investigations of the possibilities posed by nitrogen centered radicals, and the concept of radical mediated reorganizations of simple hydrocarbon frameworks into more complex and less readily accessible isomeric structures. The following areas will be investigated: a) Cyclopropylcarbinyl radicals in synthesis; b) Vinyl oxiranes, alkoxy radical trapping; c) Serial radical reactions--vinyl oxiranes as radical traps; d) Serial radical reactions--radical catalysis of hydrogen skeletal reorganizations; e) Nitrogen centered radicals; f) A "second generation" route to pseudomonic acid C; g) An allylstannane based route to coriolin; and h) Free radical alternatives to "conjugate addition-enolate trapping".
