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项目提供的资金，探索n -杂环碳化合物的有机催化作用。具体来说，Stetter反应，一种非常有用的合成转化，将在气相中进行探索。在无溶剂的情况下，对该反应进行考察，将揭示其机理细节。这个项目代表了基础科学，它很适合本科生和研究生科学家的教育。指导和培训在科学领域代表性不足的学生也将是这个项目的一部分。n-杂环碳烯（NHCs）是一种稳定的碳烯，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；作为一系列有机转化的催化剂；以质子化的形式，作为环境“清洁”的有机反应的非挥发性溶剂（离子液体）。尽管NHCs被广泛使用，但它们的基本反应性还没有很好地表征。在提出的工作中，NHCs的反应性将通过Stetter反应的研究来表征。Stetter是一种非常有用的合成转化，涉及使用NHCs作为催化剂。其机制尚不清楚，并且由于中间体的反应性，特别是在溶液中，很难探测。通过气相实验和理论方法的使用，噻唑苄基在Stetter反应中的本征反应性将被检查，以回答具体的机理问题。对Stetter反应机理的了解将有助于该反应催化剂的开发。

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.