Computational Studies of Lithium Dialkylamide Mixed Aggregates in Enolization Reactions

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The objective of this work is to use ab initio calculations to determine the mechanisms leading to the observed stereochemistries from enolate condensation reactions. Lithium dialkyl amide bases are used for enolate generation and these form mixed aggregates in solution. Geometry optimization will be performed on each observed and suspected mixed aggregate using both microsolvation and bulk solvation models. Geometry optimization will then be repeated for lithium aggregate-ketone or ester complexes to determine relative activation energies leading to stereoisomeric enolates. Enolate condensations are one of the most important carbon-carbon bond forming reactions available to organic chemists and this work should lead to a better understanding of the mechanisms of those reactions.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Lawrence M. Pratt of the Department of Chemistry at Fisk University. Dr. Pratt will use molecular modelling and calculations to better understand a class of chemical reactions know as enolate condensation reactions. Enolate condensations are one of the most important carbon-carbon bond forming reactions available to organic chemists and this work should lead to a better understanding of how those reactions are occurring. Students trained as a result of working on this project will gain experience in theoretical organic chemistry and molecular modelling, hence they will have skills needed by the pharmaceutical and speciality chemicals industries.