| A new strategy for the catalysis of organic transformations using iminium ion activation has been developed. Using this strategy, the first asymmetric organocatalytic Diels-Alder reaction has been developed. This methodology has demonstrated the possibility of an imidazolidinone salt to function as an effective asymmetric catalyst for a wide variety of chemical transformations.; The iminium ion activation strategy has also proved successful for conjugate additions, and an asymmetric organocatalytic Mukaiyama-Michael reaction has been developed using the principles of LUMO-lowering catalysis. A more reactive and selective chiral imidazolidinone catalyst was developed, and this secondary amine has extended the range of transformations possible with iminium ion catalysis.; Progress has been made towards the development of an enantioselective organocatalytic alpha-oxidation of ketones. Proline catalysis has been demonstrated to effectively catalyze the asymmetric alpha-oxidation of cyclohexanone, but extension of this methodology to other ketones has not been successful. These studies have further demonstrated the utility of proline as a catalyst, and provide a platform for the extension of HOMO-raising catalysis to other organic transformations. |
