The Synthetic Organic Program is funding Dr. Paul Helquist of the Department of Chemistry at the University of Notre Dame to continue his research on new methods in synthetic organic and organometallic chemistry. The important unifying themes among the subprojects are the construction of carbocyclic ring systems, the development of organometallic reagents with a special emphasis on transition metals, and the development of reactions that take place with asymmetric induction. First, iron-carbene complexes will be studied to test the ability of these reactive intermediates to undergo C-H insertion and cationic olefinic cyclization. Chiral-at-iron derivatives will be used to test aysmmetric versions of the reactions. Second, intermediates derived from the reaction between ketone enolates and cyclopropane derivatives will be used as precursors cyclopentanone annulation, formation of polycyclic fused cycloheptanone systems and three-carbon segments for the synthesis of large-ring systems. Third, the concept of diastereofacial selective coordination of alkenes and the subsequent use of the coordinated alkenes for chiral synthesis will be extended to include organic pi-donor ligands in general.
