CAREER: Synthesis Through Decarboxylative Metallation

本研究项目致力于开发催化脱酸金属化(通过二氧化碳挤出将金属羧酸盐转化为金属烷基)作为一种获得反应性过渡金属试剂的方法。脱羧基金属化法有望为直接从羧酸衍生物合成合成有用的有机金属试剂提供一种有效的策略。这个项目将探索基于脱羧基金属作用概念的各种综合有用的偶联反应的发展，包括脱羧基烷基化、胺化和硒化。还将探索脱羧基烯烃插入反应，其中金属催化亲电烯烃取代酯衍生物中的CO2单元。决定金属脱羧化速率的因素(空间、电子、配位能力)将被确定。课堂上将引入同辈主导的讨论小组，促进不同学生群体之间形成学习关系，并加强对化学概念的理解。研究生和本科生将通过以食物为基础的实验向当地社区的孩子介绍化学。在有机和高分子化学项目这一职业奖项的支持下，堪萨斯大学化学系的乔恩·A·通格教授正在探索在温和条件下产生活性物种的新方法，并正在开发控制合成有用有机分子的新方法。这项研究有望提高我们对化学反应的基础知识，并将为合成化学家提供环境友好(绿色)的方法来合成化合物，这些化合物是制备与药物相关的天然产物和小分子的重要中间体。此外，拟议的研究还将为本科生和研究生的培养提供基石。在课堂上，同辈主导的讨论小组不仅可以在不同的学生群体之间建立友谊，还可以增进对化学的概念理解。为了整合研究和教育经验，研究生和本科生将通过以食物为基础的实验向当地社区的儿童介绍化学，旨在激发和保持对化学的兴趣。

This research project addresses the development of catalytic decarboxylative metallation (conversion of a metal carboxylate to a metal alkyl through extrusion of carbon dioxide) as a method for accessing reactive transition metal reagents. Decarboxylative metallation is expected to provide an efficient strategy for the formation of synthetically-useful organometallic reagents directly from carboxylic acid derivatives. This project will explore the development of a variety of synthetically useful coupling reactions based on the concept of decarboxylative metallation, including decarboxylative alkylations, aminations, and selenylations. Decarboxylative alkene insertion reactions, wherein a metal catalyzes the replacement of the CO2 unit within an ester derivative by an electrophilic olefin, will also be explored. The factors (sterics, electronics, coordinating ability) that determine the rates of decarboxylative metallation will be determined. Peer-led discussion groups will be introduced in the classroom, facilitating the formation of learning relationships between diverse groups of students and enhancing conceptual understanding of chemistry. Graduate and undergraduate students will introduce children of the local community to chemistry through food-based experiments.With the support of this CAREER award from the Organic and Macromolecular Chemistry Program, Professor Jon A. Tunge, of the Department of Chemistry at the University of Kansas, is exploring new methods for the generation of reactive species under mild conditions and is developing new methods for the controlled synthesis of useful organic molecules. This research is expected to advance our fundamental knowledge of chemical reactions and will provide synthetic chemists with environmentally benign (green) methods for the synthesis of compounds that are important intermediates in the preparation of medicinally relevant natural products and small molecules. In addition, the proposed research will also provide a cornerstone for the training of undergraduate and graduate students. In the classroom, peer-led discussion groups will not only produce friendships between diverse groups of students but also enhance conceptual understanding of chemistry. In the interest of integrating research and education experiences, graduate and undergraduate students will introduce the children of the local community to chemistry through food-based experiments designed to stimulate and retain interest in chemistry.