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Title: Development and applications of rhodium-catalysed reactions to explore the synthesis of heterocycles
Author: Niu, Jingze
ISNI:       0000 0004 6497 0583
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2016
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This thesis, submitted for the degree of Doctor of Philosophy in Organic Chemistry, documents new methodologies towards the synthesis of saturated heterocycles. These methods utilise a variety of novel S- and N-chelating alkenyl aldehyde substrates, and exploit a Rh(I)-catalytic system for the coupling of these aldehydes with alkynes, alkenes and boronic acids. Chapter 1 presents a literature review surveying the development of both intramolecular and intermolecular rhodium-catalysed hydroacylation, paying particular attention to the use of chelating substrates to promote hydroacylation and suppress the decarbonylation process. The importance of N-heterocycles in pharmaceutical and natural products is also documented. Chapter 2 demonstrates the use of heterocycle-derived β-S-enals as bifunctional substrates in a rhodium-catalysed hydroacylation/Suzuki coupling sequence, resulting in the three-component assembly of heterocyclic product. An intensive study of the derivatization of the substituted heterocyclic products is also described. Chapter 3 presents a kinetic resolution study on tropane derivatives using the rhodium-catalysed alkyne hydroacylation reaction. A wide range of chiral phosphine ligands and a variation of reaction conditions and chelating groups have been explored. Chapter 4 documents an investigation of the rhodium-catalysed hydroacylation reaction using N-chelating alkenyl aldehyde substrates. A variety of β-aminoenal precursors were obtained using the Buchwald-Hartwig amination. The optimisation of the reaction conditions using various bis-phosphine ligands with different chelating groups has been documented. A brief alkyne and alkene component scope is also included. Chapter 5 documents the experimental data. Appendix presents 1H, 13C and 19F NMR spectra of novel compounds and chiral HPLC data.
Supervisor: Willis, Michael Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available