New Chemistry of Lithium Trimethylsilyldiazomethane

三甲基硅基重氮甲烷锂的新化学

• 批准号: 0955972
• 负责人: Daesung Lee
• 金额: $ 40.5万
• 依托单位: University of Illinois at Chicago
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2010
• 资助国家: 美国
• 起止时间: 2010-09-01 至 2014-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0955972&HistoricalAwards=false
• 关键词: New; Chemistry; Lithium; Trimethylsilyldiazomethane

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.

仔细分析了由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，发现了被忽视的反应性。伊利诺伊大学芝加哥分校的李大生博士和他的同事们致力于开发亚烷基卡宾的选择性图谱，开发基于这种选择性趋势的新的有价值的合成方法，并从新的机理上理解它们的反应。在化学系化学合成计划的支持下，将开发新的CH2同系化和扩环化学，同时获得关于C-C键迁移的区域选择性的新信息。将研究前所未有的亚烷基卡宾的反应性，以开发合成烯丙烯的新方法。我们将研究卡宾插入反应的区域选择性的基本方面。此外，还将探索由亚烷基卡宾前体生成的应变亚甲基环丙烷体系的反应性和选择性及其在环加成反应中的应用。对某些活性中间体如不饱和卡宾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来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方面的培训，并为他们在学术界或工业环境中的职业生涯做好准备。