Thesis advisor: Jeffrey A. Byers / Chapter 1: There are a limited number of examples of metal-catalyzed Brook rearrangements in the literature, none of which involve ruthenium, rhodium, or iridium which are common ketone hydrogenation catalysts. The content of this chapter introduces the traditional Brook rearrangement and its advantages and disadvantages in chemical synthesis. Furthermore, the few examples of metal-catalyzed Brook rearrangements of acylsilanes and structurally similar moieties are discussed. Chapter 2: Utilizing a Brook rearrangement under hydrogenation or transfer hydrogenation conditions opens up a new area of catalytic reactivity that has not been fully explored. To our knowledge, metal complexes based on ruthenium and rhodium have never been shown to catalyze a Brook rearrangement of acylsilanes. This chapter describes the mechanistic implications of a Brook rearrangement under hydrogenation or transfer hydrogenation conditions as well as the first example of a ruthenium-catalyzed Brook rearrangement of aryl acylsilanes. Chapter 3: Pioneering work performed by Jeffrey Johnson and co-workers in the area of catalytic coupling of acylsilanes and various electrophiles showed that formation of new C-C bonds through a Brook rearrangement can be a powerful synthetic tool. In this chapter, we investigate an intermolecular coupling of aryl acylsilanes and aldehydes through a metal-catalyzed Brook rearrangement under transfer hydrogenation conditions to yield two synthetically useful motifs, specifically oxygenated bicyclic compounds. A reaction screen was performed on the coupling capabilities of these two species with various ruthenium and rhodium catalysts. The result of the screen was synthesis of a silyl ether acetal through employing the starting material as the reducing equivalent. Additionally, mechanistic insight was gained to further develop the proposed methodology. Chapter 4: An intramolecular approach to achieving coupling of acylsilanes and many different types of electrophiles was envisioned as a way of furnishing synthetically useful bicyclic compounds in one step. The focus of this chapter is the synthesis of a novel acylsilane that we proposed could undergo an intramolecular cross coupling reaction under transfer hydrogenation conditions. The conclusion of this chapter outlines the future direction of the project, which entails a new route to an intermolecular cross coupling of acylsilanes and various electrophiles. Published work from Michael Krische's laboratory helped us envision a different type of acylsilane, specifically an α,β-unsaturated acylsilane, in which binding to a metal center would proceed through a π-allyl intermediate. Ongoing efforts in the coupling of α,β-unsaturated acylsilanes with electrophiles are currently underway. / Thesis (MS) — Boston College, 2013. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Microwave-Assisted Thermolysis of ortho-Substituted Aroylsilanes Marc Tremblay Master of Science Department of Chemistry University of Toronto 2008 The microwave-assisted thermolysis of ortho-substituted aroylsilanes has been investigated. When irradiated at 250ºC in DMSO or o‑dichlorobenzene for 10 minutes, aroylsilanes form siloxycarbenes that react following different pathways depending on the solvent and the structure of the starting material. It is shown that in the case of substrates having an O‑allyl or an O‑propargyl chain ortho to the acylsilane, cycloaddition occurs followed by a cascade ring opening to give respectively chroman‑4-one and chromen‑4-one derivatives in up to 66% yield. Among the major competitive pathways were the insertion of the siloxycarbene into allylic C–H bonds and decomposition of the acylsilane group to the corresponding aldehyde, followed by Claisen rearrangement.

Microwave-Assisted Thermolysis of ortho-Substituted Aroylsilanes Marc Tremblay Master of Science Department of Chemistry University of Toronto 2008 The microwave-assisted thermolysis of ortho-substituted aroylsilanes has been investigated. When irradiated at 250ºC in DMSO or o‑dichlorobenzene for 10 minutes, aroylsilanes form siloxycarbenes that react following different pathways depending on the solvent and the structure of the starting material. It is shown that in the case of substrates having an O‑allyl or an O‑propargyl chain ortho to the acylsilane, cycloaddition occurs followed by a cascade ring opening to give respectively chroman‑4-one and chromen‑4-one derivatives in up to 66% yield. Among the major competitive pathways were the insertion of the siloxycarbene into allylic C–H bonds and decomposition of the acylsilane group to the corresponding aldehyde, followed by Claisen rearrangement.

This thesis presents a new developed method for first intermolecular aldehyde/ketone cross benzoin coupling. Protected &amp / #945 / -keto tertiary alcohols are synthesized starting from easily available acyl phosphonates and ketones via Brook rearrangement in the presence of catalytic amount of cyanide ion. The scopes and the limitations of the methods for the synthesis of tertiary alcohols with &amp / #945 / -keto group are discovered.