The specific aim of this program is to probe the topological interactions, and the kinetic consequences of such interactions, that occur between chiral organometallic complexes and prochiral substrates to yield enantioselective catalysis. The experimental approach is to combine molecular modelling, synthetic, and mechanistic methodologies to (1) investigate the molecular interactions responsible for the relative diastereomeric stabilities and reactivities of the well-characterized asymmetric hydrogenation catalysts, (2) expand the scope of asymmetric catalysis by organometallic complexes containing chiral diphosphines to include the asymmetric hydrogenation of simple, monodentate substraes and to include other catalytic transformations (e.g. hydroformylation, hydrogenation, hydrocyanation, etc.) through the rational design of new chiral diphosphine ligands, and (3) push forward the development a new catalytic transformation, olefin amination. The development of asymmetric synthetic techniques is crucial for the development and production of pharmacologically active chemicals, articficial sweeteners, analgesics, etc. Catalytic asymmetric transformations, particularly those transformations in which asymmetric functionalization is effected, bring economy to asymmetric syntheses. Furthermore, understanding the mechanistic features which give rise to enantioselectivity at simple catalysts increases our understanding of the mechanisms by which complex, difficult-to-study catalysts (e.g. enzymes) operate. In order to meet the long term objectives of this research, modelling, syntheses, and kinetic studies focussing on metal complexes containing the chiral diphosphine, DIPAMP, and its derivatives are suggested. Catalytic amination chemistry will be explored through fundamental investigations of N-H bond activation at electron-rich metal complexes such as phosphine- ligated, zerovalent group 8 complexes.
