Structure-Reactivity Relationships in Carbanion Chemistry

在这项由化学系化学合成计划资助的拟议研究中，康奈尔大学化学和化学生物系的David B.Colum教授将研究芳基锂和杂芳基锂的结构和反应活性。具体地说，将研究这些化合物在邻位硫化、平衡、硅烷化、亚胺加成、卤素舞蹈、亲核芳香族取代和二阴离子的氧化环化反应中的反应活性。这项工作将集中于了解最基本的反应原理，包括取代基如何影响它们的结构和它们与常用底物反应的速率。我们将研究溶剂化和聚集的作用。这些锂试剂通常用于使芳香族化合物官能化，以合成复杂的、医学上重要的分子。尽管它们被广泛使用，但人们对这些有机锂衍生物的了解很少，这可能会导致有机合成中的重大问题。因此，更好地了解这些化合物的结构和反应活性可以提高有机合成的效率，这是制药、化工和农业行业迫切需要的。在教育影响方面，该项目将为学生提供培训，包括那些在化学科学领域历来代表性不足的学生。

In the proposed research funded by the Chemical Synthesis Program of the Chemistry Division, Professor David B. Collum of the Department of Chemistry and Chemical Biology at Cornell University will investigate the structures and reactivities of aryllithiums and heteroaryllithiums. Specifically, the reactivities of these compounds in ortholithiations, equilibrations, silylations, imine additions, the halogen dance, nucleophilic aromatic substitutions, and oxidative cyclizations of dianions will be studied. The work will focus on developing an understanding of the most fundamental principles of reactivity including how substituents influence both their structures and rates that they react with commonly used substrates. The role of solvation and aggregation will be studied. These lithium reagents are commonly used to functionalize aromatic compounds for the synthesis of complex, medicinally important molecules. Despite their widespread use, such organolithium derivatives are poorly understood, which can lead to significant problems in organic synthesis. Therefore, better understanding of the structures and reactivities of these compounds could improve the efficiency of organic synthesis, which is badly needed in pharmaceutical, chemical, and agricultural industries. In terms of educational impacts, this project will provide training of students, including those from groups historically underrepresented in the chemical sciences.