Applications of Trimethylsilyldiazomethane in Synthetic Organic Chemistry

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.