RUI: Development and Study of Chiral Organocatalysts for Asymmetric Reactions

美国国家科学基金会化学部的化学催化项目支持来自德州农工大学商学院的Allan Headley教授和Bukuo Ni共同开发、合成和研究可有效加速不对称反应的均相有机催化剂的应用。这些有机催化剂的独特之处在于它们含有离子液体部分，这给催化剂带来了广泛的性质。这些离子液体支撑（ILS）的有机催化剂是可调的，它们的性质将被调整以满足各种各样的反应条件，包括在水介质中有效，因此易于回收。由于不对称碳-碳形成反应是合成有机化学的基础反应，因此将利用这些有机催化剂研究的反应包括不对称醛醇反应、Michael反应、Mannich反应和Diels-Alder反应。此外，将进行计算建模研究，以确定导致立体化学产物形成的过渡态的性质，以更好地了解涉及这些有机催化剂的相互作用的性质。从这项研究中获得的知识将通过提供基本的见解来更好地理解新类别的手性有机催化剂如何影响不对称反应的结果，并确定影响不对称合成的因素，从而推动合成有机催化领域的发展。尽管现有的催化剂可以用来完成这些转化，但本研究的有机催化剂具有可回收利用的额外优势，并且在水条件下也有效，使其成为环境友好的“绿色”有机催化剂。这些可回收的有机催化剂具有改变有机催化的潜力，特别是在大量使用催化剂的工业中。拟议的研究不仅有助于通过开发和研究新型可回收催化剂来增加我们在有机催化领域的知识，而且还将使这所主要的本科院校的学生有机会获得宝贵的研究经验。

The Chemical Catalysis Program in the Chemistry Division at the National Science Foundation supports Professor Allan Headley and co-PI Bukuo Ni from Texas A&M University-Commerce to develop, synthesize, and study application of homogeneous organocatalysts that are effective at accelerating asymmetric reactions. These organocatalysts are unique in that they contain ionic liquid moieties, which convey a wide range of properties to the catalysts. These ionic liquid-supported (ILS) organocatalysts are tunable and their properties will be adjusted to meet a wide variety of reaction conditions, including being effective in aqueous media and thus be readily recyclable. Since the asymmetric carbon-carbon forming reactions are cornerstone reactions in synthetic organic chemistry, the reactions that will be investigated utilizing these organocatalysts include the asymmetric aldol, Michael, Mannich, and the Diels-Alder reactions. In addition, computational modeling studies will be carried out to determine the nature of the transition states leading to the formation of stereochemical products to better understand the nature of the interactions involving these organocatalysts.The knowledge gained from this research will advance the field of synthetic organic catalysis by providing fundamental insights to better understand how new categories of chiral organocatalysts influence the outcomes of asymmetric reactions and also determine the factors that influence asymmetric synthesis. Even though present catalysts can be used to accomplish these transformations, the organocatalysts of this research have the added advantage of being recyclable and are also effective under aqueous conditions, making them environmentally friendly "green" organocatalysts. These recyclable organocatalysts have the potential to transform organic catalysis, especially in industry, where large amounts of catalysts are utilized. The proposed research not only serves to increase our knowledge in the field of organic catalysis through the development and study of new types of recyclable catalysts, but also will give students at this primarily undergraduate institution the opportunity to gain valuable research experience.