Catalytic asymmetric oxidation reactions by chiral-supported bimetallic nanoclusters

手性支撑双金属纳米团簇催化不对称氧化反应

• 批准号: 1662705
• 负责人: Duy Hua
• 金额: $ 39.02万
• 依托单位: Kansas State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-07-01 至 2022-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1662705&HistoricalAwards=false
• 关键词: Catalytic; asymmetric; oxidation; reactions; chiral

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.

手性负载双金属纳米团簇催化不对称氧化反应用廉价原料生产医学上重要的有机分子对于降低成本和提高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。这个过程也制造了特别重要的手性分子，这是一种以镜像形式存在的三维结构。通常，只有一种镜像结构具有医学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）学科的学生开展外展活动。具体来说，华博士的实验室正在培养研究生和本科生，并为本科生和高中毕业生提供暑期研究实习机会。目前正在关注如何吸引女性和少数族裔学生从事STEM职业，并通过提供实践研究经验来激发他们的兴趣。在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系统，该系统涉及由手性取代的聚n -乙烯基鹿蹄草二酮（cspvp）稳定的纳米团簇，如钯/金或铜/金，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簇聚合物的反应机理和可能的反应位点。各种分析技术，包括透射电子显微镜，能量色散x射线微分析和x射线光电子能谱被用于表征。研究了改性CSPVP和纳米团簇对映体选择性的优化。Hua组也在研究催化氧化反应的范围，将其应用于中等大小分子的氧化和生物活性分子的全合成。总合成靶标包括费比氨酸、环己酸、环己酮和克拉维酮I，而区域选择性C-H氧化靶标包括氨溴胺、青蒿素、n -甲基- d -天冬氨酸受体抑制剂、美刚胺、石竹烯和脱氢枞胺。这些反应被认为是绿色的，因为使用了催化量的环境友好的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，专注于招募女性和未被充分代表的少数民族进入STEM领域，并为小型学院的本科生和附近的高中毕业生提供暑期实习机会，这支持了项目的广泛影响。

项目成果

A One-Pot Intramolecular Tandem Michael–Aldol Annulation Reaction for the Synthesis of Chiral Pentacyclic Terpenes

• DOI: 10.1055/s-0039-1690521
• 发表时间: 2019-08
• 期刊: Synthesis
• 作者: Jianyu Lu;Serkan Koldaş;Huafang Fan;J. Desper;V. Day;D. Hua

Synthesis of 1,3,4-Oxadiazoles as Selective T-Type Calcium Channel Inhibitors

选择性 T 型钙通道抑制剂 1,3,4-恶二唑的合成

• DOI: 10.3987/com-19-s(f)5
• 发表时间: 2020
• 期刊: HETEROCYCLES
• 影响因子: 0.6
• 作者: H. Hua, Duy;Simon Xie, Xinmin;Zhang, Man;Zou, Bende;J. Gunaratna, Medha;Weerasekara, Sahani;Tong, Zongbo;D. T. Nguyen, Thi;Koldas, Serkan;S. Cao, William
• 通讯作者: S. Cao, William