Thesis
Palladium-catalysed desulfinative cross-coupling reactions: Leveraging mechanistic insights for reaction optimisation
- Abstract:
-
In this thesis, the mechanism of the palladium-catalysed desulfinative cross-coupling of aryl bromides and (hetero)aryl sulfinate salts is investigated. The challenges that must be overcome to deliver improved, lower temperature versions of this process are discussed, and optimisation work based on these mechanistic insights is presented.
Chapter 1 is a literature review surveying the use of sulfinate salts in palladium-catalysed cross-coupling reactions. Particular emphasis is placed on the mechanism of these transformations and the structure of palladium sulfinate intermediates.
Chapter 2 describes the mechanistic studies of the palladium-catalysed desulfinative cross-coupling of 1-bromo-4-fluorobenzene and (hetero)aryl sulfinate salts. 2-Pyridyl and carbocyclic sulfinate substrates are compared, and different catalyst resting states and turnover limiting steps are established for the two classes of reagent. The role of the carbonate additive and the reduction of the palladium(II) precatalyst is also investigated.
Chapter 3 demonstrates the significance of the challenges associated with developing lower-temperature desulfinative cross-coupling reactions. A survey of a number of reaction parameters and their influence on the outcome of the reaction is presented.
Chapter 4 focuses on the use of the Xantphos ligand and the synthesis of Xantphos derivatives to promote desulfinative cross-coupling reactions at 100 °C.
Chapter 5 discusses the development of a desulfinamidative cross-coupling reaction using a primary aryl sulfinamide as the nucleophilic coupling partner. The feasibility of this process is demonstrated, and initial optimisation results are presented.
Chapter 6 discusses the conclusion of the research and the potential for future work.
Chapter 7 presents the experimental data.
Actions
Authors
Contributors
- Institution:
- University of Oxford
- Division:
- MPLS
- Department:
- Chemistry
- Sub department:
- Organic Chemistry
- Oxford college:
- Lincoln College
- Role:
- Supervisor
- ORCID:
- 0000-0002-0636-6471
- Funding agency for:
- De Gombert, A
- Grant:
- 1797010
- DOI:
- Type of award:
- DPhil
- Level of award:
- Doctoral
- Awarding institution:
- University of Oxford
- Language:
-
English
- Keywords:
- Subjects:
- Deposit date:
-
2021-06-20
Terms of use
- Copyright holder:
- de Gombert, A
- Copyright date:
- 2021
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