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.
