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.

通过钯催化的酮的 α-杂芳基化发生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不断增长。钯催化的反应非常有用，用于许多不同的化学领域，例如基础化学品、染料、有机发光二极管、作物保护化学品和药剂。为了进一步改进和扩展这些催化反应，必须对基础化学有一个基本的了解，以便发现新的化学转化、产生更少的副产物并产生更少的废物。在这个项目中，马丽丽博士正在研究两种类型的钯催化：氧化反应和多米诺骨牌（连续反应步骤）反应。光谱技术被用来了解这些反应的基本步骤，并且它们在绿色化学、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，例如国际暑期研究实习计划和针对没有研究经验的学生的UR-STEM暑期研究计划。马博士还积极参与STEM外展活动，例如小学生STEM日、STEM博览会日以及周六获得奖励知识计划（SPARK），以改善小学生和高中生的教育。在化学系化学催化项目的资助下，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 á-杂芳基化来实现不寻常的氧化反应和多米诺骨牌反应。正在研究的第一个反应是 Pd 催化、微波辅助合成 1,2-二酮。 1,2-二酮产品用于合成多功能结构单元，包括杂环、二胺和二亚胺。正在研究的第二个反应是钯催化微波辅助的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为获得构建模块提供了便利，这些构建模块可用于从材料化学到药物化学的各种应用。催化循环的研究正在使用 1H 和 31P NMR 技术进行探索，以深入了解反应机制。马博士是 STEM 研究和推广项目的积极参与者。为了支持该项目的更广泛影响，她与系和大学 STEM 项目结合的研究活动为招募和留住 STEM 学科的女学生、第一代大学生和非裔美国人/拉丁裔研究生提供了机会。

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