CAREER: Synthesis Through Decarboxylative Metallation

该研究项目致力于开发催化脱羧金属（通过挤出二氧化碳将金属羧酸盐转化为金属烷基）作为获得反应性过渡金属试剂的方法。脱羧金属化反应有望为直接从羧酸衍生物合成有用的有机金属试剂提供一种有效的策略。本计画将探讨以脱羧金属化的概念为基础，发展各种合成上有用的偶合反应，包括脱羧烷基化、胺化及硒化。还将探索脱羧烯烃插入反应，其中金属催化酯衍生物内的CO2单元被亲电烯烃取代。将确定决定脱羧代谢速率的因素（空间、电子、协调能力）。同侪领导的讨论小组将在课堂上引入，促进不同群体的学生之间的学习关系的形成，并提高化学的概念理解。研究生和本科生将通过食品实验向当地社区的儿童介绍化学。在有机和高分子化学计划的职业奖的支持下，Jon A.堪萨斯大学化学系的Tunge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。这项研究预计将推进我们的化学反应的基础知识，并将提供合成化学家与环境友好（绿色）的方法，用于合成化合物，这些化合物是制备药用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，同侪领导的讨论小组不仅会产生不同群体的学生之间的友谊，但也提高了化学概念的理解。为了整合研究和教育经验，研究生和本科生将通过旨在激发和保持化学兴趣的食品实验向当地社区的儿童介绍化学。

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.