Chiral Catalyst Development and Applications

本工作的目的是制备新的手性羧氨酸酯配体及其镝(II)配合物，并将其用作各种有机转化的不对称催化剂。手性催化剂将首先用于不对称的C-H插入反应。然后，将二氢呋喃(II)甲酰胺盐固定在固体载体上，用于环丙烷化反应和C-H插入催化剂。然后将金属催化的重氮化合物反应用于杂环合成，还将研究金属催化的重氮化合物的大环化反应。最后，这些化合物将被用作温和的Lewis酸催化剂，用于不对称的杂Diels-Alder反应和其他Lewis酸催化的有机转化。通过这一奖项，有机和高分子化学项目支持了亚利桑那大学化学系迈克尔·P·道尔博士的研究。多伊尔博士将探索含有被称为重氮基的官能团(反应部位)的化合物的立体选择性金属催化反应。重氮化合物可以被金属催化剂诱导失氮，从而为新的碳-碳键形成反应提供底物。催化剂形成手性口袋，在那里发生键形成反应，只形成产品的两个可能的立体异构体中的一个。在手性分子中形成碳-碳键的能力(有两个不可重叠的镜像)并且只形成两种可能形式中的一种(单一对映体)是当今制药业面临的最重要的问题之一。在这项工作过程中接受培训的学生将获得制药业所需的技能，制药业现在生产许多单一的对映体化合物。

The objective of this work is to prepare new chiral carboxamidate ligands and their dirhodium (II) complexes, then use these complexes as asymmetric catalysts for a variety of organic transformations. Chiral catalysts will first be used for enantioselective C-H insertion reactions. Dirhodium (II) carboxamidates will then be attached to solid supports and used for cyclopropanation as well as C-H insertion catalysts. Metal catalyzed reactions of diazo compounds will then be used for heterocycle synthesis and metal catalyzed macrocyclizations of diazo compounds will also be studied. Lastly, these dirhodium (II) carboxamidates will be used as mild Lewis acid catalysts for enantioselective hetero Diels-Alder reactions and other Lewis acid catalyzed organic transformations. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Michael P. Doyle of the Department of Chemistry at the University of Arizona. Dr. Doyle will explore stereoselective, metal catalyzed reactions of compounds which contain a functional group (reactive site) known as a diazo group. Diazo compounds can be induced to lose nitrogen by metal catalysts thereby providing substrates for new carbon-carbon bond forming reactions. The catalysts form chiral pockets where the bond forming reactions occur and only one of two possible stereoisomers of the product is formed. The ability to form carbon-carbon bonds in molecules which are chiral (have two nonsuperimposable mirror images) and make only one of the two possible forms (a single enantiomer) is one of the most important problems facing the pharmaceutical industry today. Students trained during the course of this work will gain skills needed by the pharmaceutical industry which now produces a number of single enantiomer compounds.