Silylene Transfer: New Silylene-Mediated Multi-Step Reactions for Stereoselective Synthesis and the Development of a New Diarylsilylene Transfer Reagent

This dissertation describes new methodology in the context of metal-catalyzed silylene transfer. Silacyclopropanation of allenes led to the discovery of isolable alkylidenesilacyclopropanes, and synthetically useful transformations were realized by carbonyl insertion reactions through allylic transposition. Asymmetric syntheses of homoallylic alcohols by this method are described. Metal-catalyzed carbon-carbon bond insertion reactions with isolated alkylidenesilacyclopropanes are discussed as general and selective new reactions. Silylene transfer to allylic sulfides and other allylic heteroatom species was investigated, and a new 1,2-sulfide migration reaction was observed to afford silacyclobutanes. Synthetic utility of the resultant silacyclobutanes was studied using carbonyl insertion reactions, but remains limited. Efforts to increase the synthetic utility of di-tert-butyl silacyclic compounds led to the discovery of a 7-silanorbornadiene as a new reagent for metal-catalyzed diarylsilylene transfer. Progress toward new multi-step silylene transfer reactions is discussed, describing silylene transfer reactions with aryl carbonyl compounds and methylenecyclopropanes.