Gas-Phase Studies of Organic Reaction Mechanisms: Stereochemistry, Eliminations, and Catalytic Intermediates

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The research will employ a combination of experimental and computational techniques to study fundamental organic reactions in the gas phase. Although it is well accepted that gas-phase methods can provide important insights into the mechanisms of organic processes, investigations of reaction stereochemistry have been limited because mass spectrometry provides limited 3-dimensional structural information. In this work, Professor Gronert will overcome this problem by using isotopic-labeling strategies to identify the stereochemical preferences of elimination and catalytic cyclopropanation reactions. Both processes play pivotal roles in organic synthesis and have been the subject of numerous studies in solution. In the catalytic reactions, the studies will take advantage of the ability of mass spectrometry to isolate and study model intermediates that are too reactive to be characterized in solution. Two key goals in the work are (1) identifying intrinsic (i.e., solvent-free) reaction preferences and (2) establishing correlations between behavior in the gas-phase and solution. This information is critical for understanding the role that mass spectrometry can play in the development of new reagents and catalysts.With this Research Award, the Organic and Macromolecular Chemistry Program supports the research of Scott Gronert of Virginia Commonwealth University. Professor Gronert is using mass spectrometry to study organic reactions in the gas phase. This approach eliminates complicating interactions with solvent molecules and can reveal the fundamental factors that govern the course of the reaction process. The mass spectrometry data will be compared with those from computational modeling and provide information on the reliability of computational models in catalytic systems. The results from this project can be used in the development of new, cost-efficient methods for rapidly assessing the capabilities of potential catalysts for organic synthesis. Student training and involvement is integrated into the project and the participants will gain valuable experience with modern instrumentation and chemical techniques.