RUI: gamma-C-Alkylation of 1,3-Dicarbonyl Compounds using Equilibrating Conditions

在这个由化学系化学合成计划资助的项目中，布拉德利大学的Brad Andersh教授和Wayne Bosma教授将使用合成和计算化学的串联方法来研究1，3-二羰基化合物使用碳酸盐和醇盐等平衡碱进行伽马碳烷基化反应的机理、范围和限制。具体的机理问题是：(1)当使用平衡碱时，为什么发生伽马烷基化而不是α-烷基化；(2)1，3-二羰基化合物的伽马-阴离子是如何形成的。开发具有成本效益和环境安全的化学工艺是化学界的一个重点领域。这项拟议研究的目标是了解和开发一种新的方法，在一个或多个类似的位置选择性地修饰有机化合物。拟议的方法在程序上比现有方法更简单，并将允许新的更绿色的化学过程。该项目的更广泛影响包括(1)让科学家更好地了解这种绿色方法，以及(2)通过为本科生和高中生提供研究机会来培养未来的科学家。

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professors Brad Andersh and Wayne Bosma of Bradley University will use a tandem approach of synthesis and computational chemistry to investigate the mechanism and the scope and limitations of gamma-carbon-alkylation reactions of 1,3-dicarbonyl compounds using equilibrating bases such as carbonates and alkoxides. The specific mechanistic questions that will be addressed are: (1) why gamma-alkylation rather than alpha-alkylation occurs when an equilibrating base is used and (2) how the gamma-anion of a 1,3-dicarbonyl compound forms. The development of chemical processes that are cost-effective and environmentally safe is an area of emphasis in the chemical community. The goal of the proposed research is to understand and exploit a new method for selectively modifying organic compounds at one or more similar sites. The proposed methodology is procedurally less complex than existing methods and will allow for new greener chemical processes. The broader impacts of the project include (1) providing scientists with a greater understanding of this green method, and (2) the training of future scientists by providing research opportunities for undergraduate and high school students.