Catalytic asymmetric oxidation reactions by chiral-supported bimetallic nanoclusters

手性支载的双金属纳米簇催化不对称氧化反应利用廉价的原料生产医药中重要的有机分子对于降低成本和改善环境可持续性具有重要意义。在这个项目中，堪萨斯州立大学的华博士正在开发一种新的催化过程，利用空气中的氧气来制备这些有价值的分子。这一过程还制造了特别重要的手性分子，这是以镜像形式存在的三维结构。通常，只有一个镜像结构具有医疗应用所需的生物活性。该项目还包括向科学、技术、工程和数学(STEM)学科的学生开展外联活动。具体来说，华博士的实验室正在培养研究生和本科生，并为本科生和高三学生提供暑期研究实习机会。在化学系化学催化项目的资助下，堪萨斯州立大学的华博士正在开发一种新的手性催化剂体系，该体系包含由手性取代的聚N-乙烯基吡咯烷酮(CSPVP)稳定的钯/金或铜/金纳米团簇，用于催化多元醇、烯烃和烷烃的不对称氧化。华的实验室正在研究纳米团簇聚合物的反应机理和可能的反应部位。包括透射电子显微镜、能量色散X射线显微分析和X射线光电子能谱在内的各种分析技术正被用于表征。通过对CSPVP和纳米团簇的修饰来优化对映体的选择性。华为集团还在研究催化氧化反应的范围，应用于中等分子的氧化和生物活性分子的全合成。总的合成目标包括蚕豆氨酸、香草酸、香草酮和棒曲酮I，而区域选择性的C-H氧化目标包括氨溴索、青蒿素、N-甲基-D-天冬氨酸受体抑制剂、美金刚、石竹烯和脱氢松香胺。这些反应被认为是绿色的，因为使用了催化量的对环境无害的CSPVP和来自铜、钯、金或铁的纳米团簇。华博士积极参与STEM外展项目，重点招聘女性和代表性不足的少数族裔进入STEM领域，并为小型学院的本科生和附近的高三学生提供暑期实习机会，这支持了该项目的更广泛影响。

Catalytic Asymmetric Oxidation Reactions by Chiral-Supported Bimetallic NanoclustersThe 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.