Biomimetic and Polymeric Catalysis in Water

在化学系有机动力学项目的支持下，哥伦比亚大学的罗纳德布雷斯洛教授将进行一项长期计划的研究，该计划旨在开发受酶催化原理启发的实用反应催化剂。最近提出的工作的切割器方面是这些设计的催化剂，显示出显着的化学，区域，和/或立体选择性的实用性。拟议的工作将包括使用树枝状聚合物为基础的试剂，已被证明提供高营业额和独特的底物选择性的各种吡哆胺催化反应。研究将扩大到包括硫胺素催化以及。这些系统提供了通过常规手段难以获得的独特反应环境。这些反应的不对称变体将使用手性特异性碱催化进行，该催化提供了良好但不是压倒性的对映体诱导。这项工作的优势是在提供创新的反应催化和实际应用之间的正确平衡。有机和高分子化学计划支持哥伦比亚大学的罗纳德布雷斯洛教授，他将试图展示在水溶液中发挥作用的实用合成方法的发明如何对环境友好，并且在许多方面比传统的有机溶剂更方便。这项工作有明显的环境影响，因为它的成功允许使用环境友好的水进行化学转化。生物化学家和学生将从这项工作中学习一般原理。验证过渡态几何结构的理论预测将加强计算化学领域，并增加对酶促反应中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如何发挥作用，并可能为开发新的更有效的方法指明方向。

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.