| This thesis discusses the development of the rhodium-catalyzed regioselective and enantiospecific allylic amination reaction, employing a range of substituted sulfonamide nucleophiles. Application to the synthesis of unnatural amino acid derivatives, mono- and disubstituted azacycles and highly functionalized aniline derivatives are also addressed. Additionally, proof of retention of configuration in the allylic amination, the effects of nucleophilicity on product distribution, as well as the examination of both matched and mismatched amination events are also discussed.; The development of first regio- and diastereoselective tandem rhodium-catalyzed allylic alkylation/Pauson-Khand reaction is also presented. The high degree of regio- and diastereocontrol obtained with this catalyst system is indicative of the potential utility of this tandem reaction sequence. A novel set of highly effective conditions has also been developed for the enantiospecific allylic alkylation reaction. Additionally, the diastereo-selecting manifold of this transformation is equally significant, as we have conducted one of the most extensive studies of the stereochemical consequences of C-2 substituted tethered enynes.; The first intermolecular Rhodium-catalyzed [4+2+2] carbocyclization reactions of tethered enynes with 1,3-butadiene are also presented herein. The optimized reaction conditions provide the first example of a crossed dimerization of an enyne with a butadiene equivalent, and show general applicability to a broad range of heteroatom-substituted tethers. A three-component tandem coupling provides a versatile method for the construction of 5,8-ring systems, which circumvents the synthesis of the enyne tether prior to cycloaddition. This tandem sequence is the second example of a temperature mediated dual function single catalyst system, which was first developed in the aforementioned Pauson-Khand reaction. |
