Mechanistic Studies of Organic Reactivity

Rutgers University New Brunswick, New Brunswick NJ

Investigators

Abstract

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.