Computational Studies of Lithium Dialkylamide Mixed Aggregates in Enolization Reactions

二烷基酰胺锂混合聚集体在烯醇化反应中的计算研究

基本信息

批准号：
0139076
负责人：
Lawrence Pratt
金额：
$ 5.7万
依托单位：
Fisk University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2002
资助国家：
美国
起止时间：
2002-01-01 至 2005-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=0139076&HistoricalAwards=false
关键词：
Computational Studies Lithium Dialkylamide Mixed

项目摘要

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.

这项工作的目的是使用从头计算来确定导致观察到的烯醇缩合反应立体化学的机制。二烷基酰胺锂碱用于生成烯醇化物，它们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怀疑的混合聚集体进行几何优化。然后对锂聚集体-酮或酯复合物重复几何优化，以确定产生立体异构烯醇化物的相对活化能。烯醇化缩合是有机化学家最重要的碳-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的机制。有机和高分子化学项目通过这一奖项支持博士的研究菲斯克大学化学系的劳伦斯·M·普拉特。普拉特博士将使用分子建模和计算来更好地理解一类称为烯醇缩合反应的化学反应。烯醇缩合是有机化学家最重要的碳-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。通过该项目接受培训的学生将获得理论有机化学和分子建模方面的经验，因此他们将具备制药和特种化学品行业所需的技能。