New Chemistry of Lithium Trimethylsilyldiazomethane

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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.