RUI: Unusual Oxidation and Domino Reactions via Palladium-catalyzed α-Heteroarylation of Ketones

RUI：钯催化的异常氧化和多米诺反应

• 批准号: 1760393
• 负责人: Lili Ma
• 金额: $ 24.3万
• 依托单位: Northern Kentucky 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: 2017-07-15 至 2022-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1760393&HistoricalAwards=false
• 关键词: RUI; Unusual; Oxidation; Domino; Reactions

Unusual Oxidation and Domino Reactions via Palladium-catalyzed alpha-Heteroarylation of KetonesThe preparation of organic chemicals using palladium catalysts continues to grow in importance in both fundamental research and industry. Reactions catalyzed by palladium are extremely useful and used in many different fields of chemistry such as basic chemicals, dyes, organic light emitting diodes, crop protection chemicals, and pharmaceutical agents. To further improve and expand these catalytic reactions, it is imperative to develop a fundamental understanding of the underlying chemistry in order to discover new chemical transformations, produce fewer byproducts, and generate less waste. In this project, Dr. Lili Ma is investigating two types of palladium-catalysis, oxidations and domino (sequential reaction steps) reactions. Spectroscopic techniques are being used to understand the fundamental steps of these reactions, and their applications in green chemistry, ligand design, biochemistry, and medicinal chemistry are also being explored. Dr. Ma is actively engaged in STEM research activities such as an international summer research intern program and UR-STEM summer research program for students without previous research experience. Dr. Ma is also highly involved in STEM outreach activities such as the STEM day for grade school students, STEM expo day, and the Saturday Program for Access to Rewarding Knowledge (SPARK) to improve the education for grade school and high school students. With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Lili Ma of Northern Kentucky University is developing palladium catalysts for unusual oxidation reactions and domino reactions via direct á-heteroarylation of ketones. The first reaction under investigation is a Pd-catalyzed, microwave-assisted synthesis of 1,2-diketones. The 1,2-diketone products are applied to the synthesis of versatile building blocks which include heterocyclic rings, diamines and diimines. The second reaction under investigation is a Pd-catalyzed microwave-assisted, one-pot domino approach for the synthesis of heteroaryl isocoumarin derivatives. These efficient organic reactions provide convenient access to building blocks which are useful for applications ranging from materials chemistry to medicinal chemistry. Studies of the catalytic cycle are being probed using 1H and 31P NMR techniques to gain insights on the reaction mechanisms. Dr. Ma is an active participant in the STEM research and outreach programs. In support of the broader impacts of the project, her research activities in conjunction with the department and university STEM programs provide opportunities to recruit and retain female students, first-generation college students and African American/Latino research students in the STEM disciplines.

钯催化的酮α-杂芳基化的异常氧化和多米诺反应使用钯催化剂制备有机化学品在基础研究和工业中的重要性继续增长。钯催化的反应非常有用，在许多不同的化学领域都有应用，如基础化学品、染料、有机发光二极管、作物保护化学品和药物制剂。为了进一步改进和扩大这些催化反应，必须对基本化学有一个基本的了解，以便发现新的化学转化，产生更少的副产品和产生更少的废物。在这个项目中，马丽丽博士正在研究两种类型的钯-催化、氧化和多米诺(顺序反应步骤)反应。光谱技术正被用来理解这些反应的基本步骤，它们在绿色化学、配体设计、生物化学和药物化学中的应用也在探索中。马博士积极参与STEM研究活动，如国际暑期研究实习生计划和为没有研究经验的学生提供的UR-STEM暑期研究计划。马博士还积极参与STEM外展活动，如为小学生举办的STEM日、STEM博览会日，以及旨在改善小学和高中学生教育的周六奖励知识获取计划(SPARK)。在化学系化学催化计划的资助下，北肯塔基大学的Lili Ma博士正在开发钯催化剂，用于通过酮的直接α-异芳基化反应进行不寻常的氧化反应和多米诺反应。研究中的第一个反应是钯催化、微波辅助合成1，2-二酮。所述1，2-二酮产品用于合成包括杂环、二胺和二亚胺在内的多种构造物。正在研究的第二个反应是钯催化的微波辅助一锅多米诺骨牌方法，用于合成杂芳基异香豆素衍生物。这些高效的有机反应提供了方便地获得构建块的途径，这些构建块对于从材料化学到药物化学的应用非常有用。正在使用1H和31P核磁共振技术探索催化循环的研究，以获得对反应机理的深入了解。马博士是STEM研究和推广计划的积极参与者。为了支持该项目的更广泛影响，她的研究活动与系和大学STEM项目一起，提供了招募和留住STEM学科中的女学生、第一代大学生和非裔美国人/拉美裔研究学生的机会。

项目成果

A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis

利用过渡金属催化的微波辅助酮直接杂芳基化

• DOI: 10.3791/60441
• 发表时间: 2020
• 期刊: Journal of Visualized Experiments
• 作者: Rosen, Alexander;Lindsay, Kara;Quillen, Andrew;Nguyen, Quynh;Neiser, Matthew;Ramirez, Stephen;Costan, Stefana;Johnson, Nathan;Do, Thuy Donna;Ma, Lili
• 通讯作者: Ma, Lili