Biomimetic and Polymeric Catalysis in Water

With the support of the Organic Dynamics Program in the Chemistry Division, Professor Ronald Breslow of Columbia University will perform research that builds upon a long-standing program that develops practical reaction catalysts that are inspired by principles of enzymatic catalysis. The cleaver aspect of the recent and proposed work is the practical nature of these designed catalyst that show notable chemo-, regio-, and or stereo selectivity. The proposed work will encompass the use of dendrimer polymer-based reagents which have been demonstrated to afford high turnover and unique substrate selectivity for a variety of pyridoxamine catalyzed reactions. Studies will be expanded to include thiamine catalysis as well. These systems provide a unique reaction environment that is difficult to obtain by conventional means. Asymmetric variants of these reactions will be pursued using chiral specific base catalysis which has provided good but not overwhelming enantio-induction. The strength of this proposed work is in providing the right balance between innovative reaction catalysis and practical application. The Organic and Macromolecular Chemistry Program supports Professor Ronald Breslow of Columbia University who will attempt to show how the invention of practical synthetic methods that function in water solution will be environmentally friendly, and in many ways more convenient than traditional organic solvents. There is an obvious environmental impact of this work as its success allows for the performance of chemical conversions using environmentally benign water. Biochemists and students will learn general principles from this work. Validating theoretical predictions of transition state geometries will strengthen the field of computational chemistry, and add to general understanding of likely pathways in enzymatic reactions. The investigation of enzyme mimics will aid in the understanding of how these complex biological catalysts function and perhaps point the way to the development of new and more efficient methodology.