Mechanistic Studies of Organic Reactivity

罗格斯大学化学系的Jeehiun凯瑟琳李教授将利用化学系化学结构，动力学机制B计划提供的资金，探索N-杂环卡宾的有机催化。 具体来说，Stetter反应，一个非常有用的合成转化，将在气相中进行探索。通过在无溶剂条件下考察该反应，将揭示其机理细节。这个项目代表了基础科学，适合本科生和研究生科学家的教育。 N-杂环卡宾（NHC）是稳定的卡宾，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;并且以质子化形式作为环境“清洁”的非挥发性溶剂用于有机反应（离子液体）。 尽管NHC被广泛使用，但其基本反应性并没有得到很好的表征。 在拟议的工作中，NHC的反应性将通过调查的Stetter反应的特点。 Stetter是一种非常有用的合成转化，涉及使用NHC作为催化剂。 其机制仍然未知，并且由于中间体的反应性，特别是在溶液中，可能难以探测。 通过使用气相实验和理论方法，在Stetter反应中噻唑亚基的固有反应性将被检查，以回答具体的机理问题。 对Stetter反应机理的理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.