Biomimetic and Polymeric Catalysis in Water

在化学系有机动力学项目的支持下，哥伦比亚大学的Ronald Breslow教授将在一个长期存在的项目的基础上进行研究，该项目受酶催化原理的启发，开发实用的反应催化剂。最近和提议的工作中最明显的方面是这些设计的催化剂的实用性，它们表现出显著的化学、区域和立体选择性。提议的工作将包括使用基于树突聚合物的试剂，这些试剂已被证明对各种吡哆胺催化反应具有高周转率和独特的底物选择性。研究也将扩大到硫胺素催化。这些系统提供了一种独特的反应环境，这是传统方法难以获得的。这些反应的不对称变体将使用手性特异性碱催化，它提供了良好的但不是压倒性的对映体诱导。这项工作的优势在于在创新反应催化和实际应用之间提供了适当的平衡。有机和大分子化学项目支持哥伦比亚大学的罗纳德·布雷斯洛教授，他将试图展示如何发明实用的合成方法，使其在水溶液中发挥作用，并且在许多方面比传统的有机溶剂更环保。这项工作对环境有明显的影响，因为它的成功允许使用无害环境的水进行化学转化。生化学家和学生将从这项工作中学到一般原理。验证过渡态几何的理论预测将加强计算化学领域，并增加对酶促反应可能途径的一般理解。对酶模拟物的研究将有助于理解这些复杂的生物催化剂是如何起作用的，并可能为开发新的更有效的方法指明道路。

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.