Palladium catalyzed C–O bond activation
| dc.contributor.author | Gaube, Gregory | |
| dc.contributor.supervisor | Leitch, David | |
| dc.date.accessioned | 2024-12-24T17:44:34Z | |
| dc.date.available | 2024-12-24T17:44:34Z | |
| dc.date.issued | 2024 | |
| dc.degree.department | Department of Chemistry | |
| dc.degree.level | Doctor of Philosophy PhD | |
| dc.description.abstract | Carboxylate C–O bonds are atom-economical, robust in synthesis, and easily accessible, but have traditionally been ineffective synthetic handles for Pd catalysis. In this thesis the utility of these cross-coupling handles in Pd catalysis has been established. As global climate issues necessitate an alternative to oil-based processes, the development of Pd-catalyzed C–O bond activation chemistry, such as the chemistry explored in this thesis, has the potential to aid in biomass becoming a common future feedstock. This thesis is divided into three research chapters. Firstly, we evaluated the mechanism of an air-stable, base-free, Pd-catalyzed cross coupling of enol carboxylates and aryl boronic acids that was first developed within the Leitch Lab. This experimental evaluation uncovered key intermediates that allowed us to propose a cationic Pd(II)-only mechanism. Secondly, the knowledge gained in evaluating the mechanism was applied to Miyaura borylation of various enol carboxylates. In this study we uncovered that the nature of the enol carboxylate and the boron source greatly impacted the reactivity in the initial synthesis as well as any future desired reactivity of the enol boronate. Finally, by identifying active pharmaceutical ingredients, specifically pyrido[1,2-a]pyrimidin-4-ones, that could be used in future C–O activation chemistry, we systematically approached their synthesis to create and characterize a library of substituted molecules. We demonstrated that we could functionalize these molecules with both pivalate and tosylate synthetic handles. Because the fundamental reactivity of these carboxylate C–O bonds is established, these three chapters have created myriad potential research projects that are discussed in Chapter 5. | |
| dc.description.embargo | 2025-12-16 | |
| dc.description.scholarlevel | Graduate | |
| dc.identifier.uri | https://hdl.handle.net/1828/20892 | |
| dc.language | English | eng |
| dc.language.iso | en | |
| dc.rights | Available to the World Wide Web | |
| dc.subject | Catalysis | |
| dc.subject | Palladium | |
| dc.subject | Organic chemistry | |
| dc.title | Palladium catalyzed C–O bond activation | |
| dc.type | Thesis |