Catalytic asymmetric oxidation reactions by chiral-supported bimetallic nanoclusters

Kansas State University, Manhattan KS

Investigators

Abstract

Catalytic Asymmetric Oxidation Reactions by Chiral-Supported Bimetallic Nanoclusters The production of organic molecules important in medicine from inexpensive raw materials is important for reducing cost and improving environmental sustainability. In this project, Dr. Hua of Kansas State University is developing a new catalytic process using oxygen from air to prepare these valuable molecules. This process is also making especially important chiral molecules, which are three-dimensional structures that exist as mirror images. Often, only one of the mirror image structures has the biological activity required for the medical application. The project is also involving outreach activities to students in science, technology, engineering and mathematics (STEM) disciplines. Specifically, Dr. Hua's laboratory is training graduate and undergraduate students, and is providing summer research internships for undergraduates and high school seniors. Attention is being paid to attracting women and minority students to STEM careers, and stimulating their interest by enabling hands-on research experiences. With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Hua of Kansas State University is developing a new chiral catalyst system involving nanoclusters such as palladium/gold or copper/gold stabilized by chiral-substituted poly-N-vinylpyrollidinones (CSPVPs) for the catalytic asymmetric oxidation of polyols, alkenes, and alkanes. Hua's laboratory is investigating the reaction mechanism and possible reactive site of the nanoclusters-polymer. Various analytical techniques including transmission electron microscopy, energy dispersive X-ray microanalysis, and X-ray photoelectron spectroscopy are being used for characterization. Optimization of the enantioselectivity by modification of CSPVP and nanoclusters is being investigated. The Hua group is also studying the scope of the catalytic oxidation reactions, with application to the oxidation of medium-sized molecules and the total syntheses of bioactive molecules. Total synthesis targets include fabianine, cyperanic acid, cyperolone, and clavulone I, while the regioselective C-H oxidation targets comprise ambroxide, artemisinin, N-methyl-D-aspartate receptor inhibitor, memantine, caryophyllene, and dehydroabietyl amine. These reactions are considered to be green, since catalytic amounts of environmentally benign CSPVPs and nanoclusters derived from copper, palladium, gold, or iron are used. Dr. Hua is actively involved in STEM outreach programs by focusing on recruitment of women and underrepresented minorities into the STEM fields and providing summer internships for undergraduates from small colleges and nearby high school seniors, which support the project's broader impacts.