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Title: Application of direct imine acylation methodology in the synthesis of nitrogen heterocycles and natural products
Author: Chambers, Sarah
ISNI:       0000 0004 6350 6033
Awarding Body: University of York
Current Institution: University of York
Date of Award: 2016
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This thesis describes the use of direct imine acylation (DIA) methodology in a range of different applications. Firstly, the attempted synthesis of (±)-cytisine is described (Chapter 2). The use of DIA methodology in the formation of the pyridone ring scaffold of (±)-cytisine has been explored. In the most advanced synthesis towards (±)-cytisine achieved in this project, the generation of N-acyliminium ions from imine A and subsequent nucleophilic addition of organometallic allyl reagents was developed to give diene B. DIA methodology has also been utilised in the synthesis of spirocyclic products from simple indole acids C and imines D (Chapter 3). The reaction provides a broad range of products E in good yields and the indole acid starting materials C are readily synthesised using Fischer indole methodology. The stereoselectivity of the reaction, derivatisation of the products E and 3D shape analysis are also described. Finally, work towards the synthesis of (±)-aspidospermidine, using the spirocyclisation methodology developed in this project, is introduced (Chapter 4). Two strategies are proposed utilising an intramolecular Heck reaction or a ring-closing metathesis to complete the polycyclic scaffold. A key DIA reaction between the synthesised acid F and imine G is reported and shows formation of the spirocyclic scaffold H.
Supervisor: O'Brien, P. A. ; Taylor, R. J. K. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available