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计划支持德克萨斯农工商业大学的Allan Headley教授和合著者Pi Bukuo Ni开发、合成和研究有效促进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，这些部分向催化剂传递了广泛的性质。这些离子液体(ILS)支持的有机催化剂是可调节的，它们的性质将被调整以满足各种反应条件，包括在水介质中有效，因此很容易回收。由于不对称碳-碳形成反应是合成有机化学中的基石反应，利用这些有机催化剂研究的反应包括不对称Aldol、Michael、Mannich和Diels-Alder反应。此外，还将开展计算模拟研究，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促进合成有机催化领域的发展，为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以及确定影响不对称合成的因素提供基础见解。尽管目前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，并且在水条件下也是有效的，使它们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转化有机催化的潜力，特别是在使用大量催化剂的工业中。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，而且还将使这所以本科为主的学院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.