RUI: Effects of Cationic Substituents on the Cope Rearrangement

RUI：阳离子取代基对 Cope 重排的影响

• 批准号: 0210498
• 负责人: Kathleen Morgan
• 金额: $ 17.4万
• 依托单位: Xavier University of Louisiana
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-08-01 至 2007-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0210498&HistoricalAwards=false
• 关键词: RUI; Effects; Cationic; Substituents; Cope

With the support of the Organic Dynamics Program in the Chemistry Division, Kathleen Morgan of the Department of Chemistry at Xavier has begun a study of the Cope Rearrangement, which is a reaction where new carbon-carbon bonds are made with high regio- and stereo selectivity, via the reorganization of a 1,5-hexadiene. The goal of this study is to determine whether the reaction rate can be accelerated with the attachment of cationic substituents on the reactive core of the system. The formation of carbon-carbon bonds is at the heart of organic chemistry, yet there are a limited number of ways to construct them. The creation of the carbon-based skeleton often represents much of the challenge in synthesis. The Cope Rearrangement has been much studied and heavily exploited in synthesis and yet we are still not able to claim that it is fully understood or that it has reached its full potential in synthetic applications. The experimental and theoretical study of the Cope rearrangement of 1,5 hexadienes bearing electron-withdrawing groups at the 3 position is a well-defined project that has the potential to yield fundamental insights into this rearrangement and extend the full synthetic utility of this reaction. Because of the importance of carbon-carbon bond making, this project creatively blends literature, theory, and wet chemistry in order to increase understanding of the chemistry and produce novel methodology. .Professor Kathleen Morgan, of the Department of Chemistry at Xavier University, with the support of the Organic Dynamics Program, will conducted her research at an historically black undergraduate university (HBCU). Undergraduates are capable of performing the majority of the proposed research. The preliminary results were obtained by more than a dozen undergraduates at Professor Morgan's previous institution. Underrepresented students will have the opportunity to participate in all aspects of this fundamental research including the synthesis of organic compounds using a series of known procedures, development of new reactions, purification and characterization of products, determination of reaction rates by spectroscopy, and computational studies.

在化学系有机动力学项目的支持下，泽维尔大学化学系的凯瑟琳·摩根开始了柯普重排的研究。柯普重排是一种通过1,5-己二烯的重组，形成具有高区域和立体选择性的新碳-碳键的反应。本研究的目的是确定在体系的反应核上附着阳离子取代基是否可以加速反应速率。碳-碳键的形成是有机化学的核心，但构建碳-碳键的方法有限。碳基骨架的制造通常是合成过程中最大的挑战。Cope重排已经在合成中得到了大量的研究和开发，但我们仍然不能声称它已经被完全理解，或者它已经在合成应用中发挥了全部潜力。实验和理论研究在3位携带吸电子基团的1,5己二烯的Cope重排是一个明确的项目，有可能产生对这种重排的基本见解，并扩展该反应的全部合成用途。由于碳-碳键制作的重要性，本项目创造性地将文献，理论和湿化学结合起来，以增加对化学的理解并产生新的方法。泽维尔大学化学系的凯瑟琳·摩根教授，在有机动力学项目的支持下，将在一所历史悠久的黑人本科大学（HBCU）进行她的研究。本科生有能力完成大部分拟议的研究。初步结果是由摩根教授之前所在机构的十几名本科生得出的。未被充分代表的学生将有机会参与这一基础研究的各个方面，包括使用一系列已知程序合成有机化合物，开发新反应，纯化和表征产品，通过光谱学确定反应速率，以及计算研究。