Asymmetric Induction in Organocopper Conjugate Addition Reactions

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This investigation will develop general, efficient methods for effecting asymmetric induction in organocopper conjugate addition reactions and formally equivalent SN2' substitution reactions. The project has four specific goals. First, several potentially effective chiral non-transferable ligands, suggested by the preliminary study, will be synthesized and examined. These include a chiral bicyclic ı3.3.0! octahydrocyclopentaıb!pyrrole ring system and a chiral binaphthyl amido ligand that may provide an electronic basis for the asymmetric induction. Second, mechanistic studies involving 1H, 13C, and 7Li NMR experiments and molecular weight determinations will be undertaken to probe the structures and compositions of the various cuprate reagents. Third, methods involving chiral transferable ligands that can be readily transformed into a variety of substituents by facile functional group manipulations will be examined. Fourth, methods involving readily prepared chiral substrates and their reactions with organocopper reagents in conjugate addition and SN2' substitution reactions will be explored. These methods involve chiral alpha, beta-unsaturated hydrazones and allylic acetals. This research was initiated at Boston University and then transferred to Clemson University. It will lead to the development of new, efficient methods for synthesizing natural products. It has resulted in nine publications.