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Title: Studies toward the application and development of rhodium-catalysed hydroacylation reactions
Author: Neuhaus, James
ISNI:       0000 0004 6498 7297
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2016
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The described in this thesis is primarily concerned with the development of Rh-hydroacylation based approaches to heterocycle synthesis. In addition to investigations on a number of heterocyclic scaffolds, work has been undertaken to increase the synthetic appeal of hydroacylation by expanding the range of functional groups that can be employed as chelating tethers. Chapter 1 is a literature review surveying the key milestones in the development of efficient, selective intermolecular hydroacylation. The use of chelating tethers, and the development of highly active ligands for their use, is detailed, as well as a summary of attempts to circumvent the requirement for such a tether using Rh and a number of other late transition metals and NHC catalyst systems. The application of a number of Rh-catalysed reactions to the synthesis of heterocycles has been discussed. Chapter 2 describes attempts to synthesise 1,3-dicarbonyl analogues, commonly used as intermediates for the synthesis of a number of five- and six-membered heterocycles. In addition, an approach to pyridines featuring a novel disconnection is also detailed. Chapter 3 presents a detailed investigation into the synthesis of diversely substituted quinolines via Rh-catalysed hydroacylation. Whilst this approach was successful across a broad range of substrates and substitution patterns, a number of minor limitations were encountered. Methods to overcome each of these drawbacks are detailed, including the synthesis of tether-free quinolines through tandem hydroacylation - C-S functionalisation protocols. Chapter 4 concerns the synthesis of N-containing heterocycles through intramolecular hydroimination. In addition to the conditions employed for intermolecular hydroacylation, a diverse range of hydroacylation catalysts was evaluated. Chapter 5 documents exploration of the use of the removable MTM-directing group. In addition to extending range of hydroacylation reactions, efforts were made to apply the methodology developed to the synthesis of the natural product sphingosine. Chapter 6 summarises the research presented and the potential for future work. Chapter 7 presents the experimental data.
Supervisor: Willis, Michael C. Sponsor: Engineering and Physical Sciences Research Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available