New Methods for Catalytic Asymmetric Synthesis of Valuable Chemicals

该项目致力于鉴定新的催化剂和催化方法，用于通过活化碳-碳π键以供外部杂原子亲核试剂攻击来制备有价值的对映体富集的非环状和杂环分子。对钯环钴恶唑啉（COP）配合物催化不对称合成对映体富集的支链烯丙基胺、酯和醚的范围进行了界定。使用这种化学构造环状分子，如内酯和环醚和氮杂环将被定义。COP催化合成对映体富集的烯丙基酯和苯酚的机理研究将进行，以促进发现改进的催化剂，并允许通过类似的途径进行新的反应的合理设计。拟议的调查的一个重要目标是确定更简单，更便宜的催化剂。使用不对称的Pd（II）和相关的催化剂的立体控制结构的杂环级联成环processes.To增加选择性和安全性，新的药物引入临床实践中越来越复杂的手性分子作为单一的对映异构体销售。有了这个奖项，有机和高分子化学计划是支持博士拉里E。欧文市加州大学化学系的奥弗曼说。奥弗曼教授和他的学生正在研究使用含钯化合物来实现手性有机分子的选择性合成。拟议的研究计划有望为制药工业提供合成和发现单一对映体药物的新工具。

This project addresses the identification of new catalysts and catalytic methods for preparing valuable enantioenriched acyclic and heterocyclic molecules through the activation of carbon-carbon pi bonds for attack by external heteroatom nucleophiles. The scope of the asymmetric synthesis of enantioenriched branched allylic amines, esters and ethers catalyzed by palladacyclic cobalt oxazoline (COP) complexes will be defined. The use of this chemistry for constructing cyclic molecules such as lactones and cyclic ethers and nitrogen heterocycles will be defined. Mechanistic investigations of the COP-catalyzed synthesis of enantioenriched allylic esters and phenols will be undertaken in order to facilitate discovery of improved catalysts and allow the rational design of new reactions that proceed by similar pathways. An important objective of the proposed investigations is to identify simpler, less expensive catalysts. The use of asymmetric Pd(II) and related catalysts for stereocontrolled construction of heterocycles by cascade ring-forming processes will also be explored.To increase selectivity and safety, new pharmaceuticals introduced into clinical practice are increasingly complex chiral molecules marketed as single enantiomers. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Larry E. Overman, of the Department of Chemistry at the University of California at Irvine. Professor Overman and his students are studying the use of compounds containing palladium to effect the selective synthesis of chiral organic molecules. The proposed program of research is expected to provide the pharmaceutical industry with new tools for the synthesis and discovery of single enantiomer drugs.