Chiral Catalyst Development and Applications

本工作的目的是制备新的手性羧酸酯配体及其配合物，然后将这些配合物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对映选择性碳氢插入反应。然后，羧酰胺Dirhodium （II）将附着在固体载体上，用于环丙烷化以及碳氢插入催化剂。金属催化重氮化合物的反应将用于杂环合成，金属催化重氮化合物的大环化也将进行研究。最后，这些羧酸二钠将作为温和的路易斯酸催化剂用于对映选择性杂diols - alder反应和其他路易斯酸催化的有机转化。有机和大分子化学项目用这个奖项来支持亚利桑那大学化学系的Michael P. Doyle博士的研究。多伊尔博士将探索立体选择性，金属催化反应的化合物，其中包含一个官能团（反应位点）称为重氮基团。重氮化合物可以通过金属催化剂诱导失去氮，从而为新的碳-碳键形成反应提供底物。催化剂在成键反应发生的地方形成手性口袋，产物的两种可能的立体异构体中只形成一种。在手性分子（具有两个不可重叠的镜像）中形成碳-碳键，并且只能形成两种可能形式中的一种（单一对映体）的能力是当今制药工业面临的最重要问题之一。在这项工作过程中训练的学生将获得制药行业所需的技能，该行业现在生产许多单一对映体化合物。

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.