New Chemistry of Lithium Trimethylsilyldiazomethane

对羰基化合物和三甲基硅基重氮甲烷锂形成的亚烷基卡宾及其前体的反应性进行了仔细的分析，发现了被忽视的反应性。伊利诺伊大学芝加哥分校的Daesung Lee博士及其同事旨在利用亚烷基卡宾的选择性特征，开发依赖于这种选择性趋势的新的有价值的合成方法，并对其反应获得新的机理理解。在化学系化学合成计划的支持下，将开发新的CH 2同系化和扩环化学，同时获得有关C-C键迁移的区域选择性的新信息。研究亚烷基卡宾前所未有的反应活性，开发合成联烯的新方法。研究了卡宾插入反应区域选择性的基本问题。此外，本论文还将探讨由亚烷基卡宾前驱体生成的应变亚甲基环丙烷体系的反应性和选择性，以及它们在环加成反应中的应用。 对某些反应性中间体如不饱和卡宾物种的反应性的新认识和对其行为的良好控制将提高化学家开发更有效的合成方法以制备复杂结构化合物（包括药用化学品）的能力，从而最终改善人类健康并产生广泛的社会影响。此外，这项研究为学生提供基础和应用化学合成的培训，并为他们在学术界或工业界的职业生涯做好准备。

A careful analysis of the reactivity of alkylidene carbenes and their precursors formed from carbonyl compounds and lithium trimethylsilyldiazomethane has led to the discovery of overlooked reactivity. Dr. Daesung Lee and coworkers at the University of Illinois at Chicago aim at exploiting the selectivity profile of alkylidene carbenes, developing new valuable synthetic methods that rely on this selectivity trend, and gaining new mechanistic understanding of their reactions. With the support from the Chemical Synthesis Program in the Division of Chemistry, new CH2 homologation and ring expansion chemistry will be developed with concomitant garnering of new information about the regioselectivity of C-C bond migration. Unprecedented reactivity of alkylidene carbenes to develop new method for allene synthesis will be investigated. The fundamental aspects of regioselectivity of carbene insertion reaction will be studied. In addition, the reactivity and selectivity of strained methylene cyclopropane systems generated from alkylidene carbene precursors and their utility in cycloaddition reaction will be explored. The new understanding of reactivity of certain reactive intermediates such as unsaturated carbene species and a good control over their behavior would improve chemists' ability to develop more effective synthetic methods to prepare compounds of complex structures (including chemicals of medicinal use), thus ultimately improve human health and have broad societal impacts. Furthermore, this research provides training for students in fundamental and applied chemical synthesis and prepares them for careers in either academia or industrial settings.