Mechanistic Studies of Organic Reactivity

罗格斯大学化学系的Jeehiun Katherine Lee教授将利用化学系化学结构、动态和机制B计划提供的资金，探索N-杂环卡宾的有机催化作用。具体地说，将在气相中探索Stetter反应，这是一种非常有用的合成转化。在无溶剂条件下考察该反应将揭示反应的机理细节。这个项目代表了基础科学，它很好地帮助了本科生和研究生科学家的教育。N-杂环卡宾(NHCs)是一种稳定的卡宾，具有广泛的应用，包括作为过渡金属催化反应的有效新型配体；本身作为催化剂，用于一系列有机转化；质子化形式，作为环境“清洁”的有机反应的非挥发性溶剂(离子液体)。尽管NHC被广泛使用，但它们的基本反应性还没有得到很好的表征。在拟议的工作中，将通过对Stetter反应的研究来表征NHCS的反应性。Stetter是一种非常有用的合成转化，涉及使用NHCS作为催化剂。其机理尚不清楚，而且由于中间体的反应性，特别是在溶液中，可能很难探索。通过使用气相实验和理论方法，将考察噻唑烷类化合物在Stetter反应中的本征反应性，以回答特定的机理问题。对Stetter机理的了解将有助于开发该反应的催化剂。

Professor Jeehiun Katherine Lee of the Department of Chemistry at Rutgers University will utilize funding provided by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division to explore organocatalysis by N-heterocyclic carbenes. Specifically, the Stetter reaction, a highly useful synthetic transformation, will be explored in the gas phase. Mechanistic details will be revealed by examining this reaction in the absence of solvent. This project represents fundamental science that lends itself well to the education of both undergraduate and graduate scientists. The mentoring and training of students underrepresented in science will also be part of this project.N-Heterocyclic carbenes (NHCs) are stabilized carbenes that have a wide variety of applications, including as effective novel ligands for transition-metal-catalyzed reactions; as catalysts in their own right, for a range of organic transformations; and in protonated form, as environmentally "clean" nonvolatile solvents for organic reactions (ionic liquids). Despite the widespread use of NHCs, their fundamental reactivity is not well characterized. In the proposed work, the reactivity of NHCs will be characterized through the investigation of the Stetter reaction. The Stetter is a highly useful synthetic transformation that involves the use of NHCs as catalysts. The mechanism remains unknown, and can be difficult to probe due to the reactivity of intermediates, particularly in solution. Through the use of gas-phase experimental and theoretical methods, the intrinsic reactivity of thiazolylidenes in the Stetter reaction will be examined to answer specific mechanistic questions. Mechanistic understanding of the Stetter will aid in the development of catalysts for the reaction.