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Applications of Trimethylsilyldiazomethane in Synthetic Organic Chemistry

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thesis
posted on 20.06.2014, 00:00 authored by Huaqing Liu
This thesis describes novel applications of trimethylsilyldiazomethane (TMSD) in synthetic organic chemistry. Part I of this work focuses on the methodology of cyclic ketone monomethylene homologation utilizing lithiated trimethylsilyldiazomethane. Subsequently, this methodology was further optimized to a more practical operation using neutral trimethylsilyldiazomethane catalyzed by the Lewis base tributylammonium triphenylsilyl difluorosilicate (TBAT) or potassium tert-butoxide. In part II of the thesis, the application of trimethylsilyldiazomethane as a C–N–N synthon in the 1,3-dipolar cycloaddition reactions is thoroughly reviewed. Then is described a novel process whereby the sequential reaction of trimethylsilyldiazomethane with 4-alkenyl ketones and aldehydes are catalyzed by Lewis bases, to form fused Δ1- and Δ2-pyrazolines. In part III of this thesis, yet another major application of trimethylsilyldiazomethane: generating alkylidene carbenes is reviewed, along with the reactions of these carbenes. Finally, is presented a novel alkylidene carbene chemistry whereby an olefin insertion/dimerization via a concerted [2 + 2] cycloaddition or involving trimethylenemethane (TMM) diradicals formed complex hydrocarbons.

History

Advisor

Lee, Daesung

Department

Chemistry

Degree Grantor

University of Illinois at Chicago

Degree Level

Doctoral

Committee Member

Gevorgyan, Vladimir Mohr, Justin Wardrop, Duncan Gomtsyan, Arthur

Submitted date

2014-05

Language

en

Issue date

20/06/2014

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