Computational Studies of Lithium Dialkylamide Mixed Aggregates in Enolization Reactions

本工作的目的是使用从头计算，以确定从烯醇化物缩合反应所观察到的立体化学的机制。 二烷基氨基锂碱用于烯醇化物的生成，并且这些在溶液中形成混合聚集体。 将使用微溶剂化和本体溶剂化模型对每个观察到的和疑似混合聚集体进行几何优化。 然后将对锂聚集体-酮或酯复合物重复几何优化，以确定导致立体异构烯醇化物的相对活化能。 烯醇化物缩合反应是有机化学家最重要的碳-碳键形成反应之一，这项工作将有助于更好地理解这些反应的机理。菲斯克大学化学系的普拉特说。 Pratt博士将使用分子建模和计算来更好地理解一类称为烯醇化物缩合反应的化学反应。 烯醇化物缩合是有机化学家可用的最重要的碳-碳键形成反应之一，这项工作应该有助于更好地理解这些反应是如何发生的。 通过该项目培训的学生将获得理论有机化学和分子建模方面的经验，因此他们将拥有制药和特种化学品行业所需的技能。

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.