Synthesis and application of nitrogen containing heterocycles

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Wakeling, Matthew G. ORCID: https://orcid.org/0000-0002-8802-7667 (2020). Synthesis and application of nitrogen containing heterocycles. University of Birmingham. Ph.D.

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Abstract

This thesis describes the exploration of trisubstituted oxazoles as building blocks in the synthesis of complex nitrogen containing heterocycles for medicinally relevant polycyclic piperidines and novel annulated nucleophilic heterocyclic carbene ligands.

The research presented discusses advancements made in a gold-catalysed cascading cycloaddition process that delivers epoxy-bridged piperidine fused polycycles through intramolecular Diels-Alder cyclisations of 4-amidooxazoles. A complementary cobalt-catalysed approach is then presented that accesses regioisomeric piperidine fused heterocycles via 5-amidooxazoles utilising chemically related catalysis precursors. The subsequent reactivity of a range of previously unknown structures is then discussed, offering rapid access into a host of diverse sp3-rich architectures including polycyclic 1,3-aminoalcohols, δ-lactams and functionalised piperidine motifs.

The gold-catalysed formal [3+2] dipolar cycloaddition is then presented as a key step in the construction of a series of oxazole annulated imidazolium salts as precursors to nucleophilic heterocyclic carbene ligands. Building on key concepts from this series, a second ligand design is then presented and realised that incorporates pyrimidine annulated imidazolium salts. Finally, the coordination chemistry of these salts to transition metals is discussed alongside analysis of the steric impact of the ligands in Au(I) complexes.

Type of Work:

Thesis (Doctorates > Ph.D.)

Award Type:

Doctorates > Ph.D.

Supervisor(s):