| Rational design of homogeneous catalysts is an ongoing challenge. The research described in this thesis attempted to come to a more complete understanding of selectivity in asymmetric hydrogenation and hydroformylation.; Despite many years of intensive study, the natures of turnover-limiting and enantiodetermining steps in catalytic asymmetric hydrogenation of prochiral enamides are poorly understood. This thesis presents an intriguing set of studies involving isotopic labelling distributions in catalytic enamide hydrogenation. The results of studies re-examining the application of isotopic probes to the catalytic hydrogenation of enamides is described. These results provide some insights into the nature of the dihydrogen activation step in enamide hydrogenation.; Chelation is a new approach to high selectivity catalysis. Covalent attachment of functionalized olefins in the secondary coordination sphere of a transition metal catalyst was found to induce selectivity. This thesis presents the synthesis, characterization, and catalytic properties of novel phosphine ligands which contains a borate moiety capable of covalently bonding to olefinic alcohols. Hydroformylation of these ligand/substrates showed moderate changes in regioselectivity. |
