Chapter 1. A brief outline, as well as a time table, of organometallic chemistry is described to better acquaint the reader with the field. Several detailed explanations of catalysis, specifically hydroamination, aryl amination, and Suzuki cross-coupling are presented in a very general context. Finally, basic principles of ligands and their design are outlined, as well as the importance of the research conducted herein.
Chapter 2. Twenty-six new α,β-unsaturated β-chloroimines were synthesized from commercially available ketones using the Vilsmeier-Haack reagent, followed by Schiff-base condensation. Each imine was subsequently converted to an α,β-unsaturated 3-iminophosphine through either late-metal catalyzed phosphorus-carbon cross-coupling or via an addition/elimination sequence. Depending on the substituents present on the vinyl group, the resultant phosphines were isolated as either E- or Z-diastereomers with successful isolation of predominately single diastereomers for all twenty-seven new phosphines investigated.
Chapter 3. Several palladium(II) 3-iminophosphine complexes were synthesized in moderate to high yield. With relevance to many palladium-catalyzed coupling reactions, these complexes incorporated a wide variety of ligands, including amines, alkyls, allyls, and triflates. The presence of both η1- and η2-coordination modes demonstrates the hemilability of the 3-iminophosphine ligand class, as determined by X-ray crystallography and NMR spectroscopy.
Chapter 4. Catalytic screening of various palladium(II) 3-iminophosphine complexes led to the generation of a wide array of products. The catalytic systems investigated were hydroamination and several cross-coupling reactions including aryl amination and Suzuki cross-coupling. The final products of the catalyses were monitored by GC for product conversion while being isolated and characterized by standard organic techniques and spectroscopy.