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Title: Novel synthetic routes towards trans-THFs and application towards the FG fragment of pectenotoxin-4
Author: Tucker, Michael J.
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2013
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trans-2,5-Disubstituted tetrahydrofurans (THFs) are a common structural motif in a multitude of biologically active natural products. This thesis explores new synthetic routes for their synthesis and subsequent application towards the C31-40 fragment of pectenotoxin-4. Chapter 1: Introduction This chapter reviews methods for the synthesis of trans-2,5-disubstituted tetrahydrofurans with a special emphasis on those that have been applied towards the synthesis of natural products. Chapter 2: Results and Discussion The Acyloin Coupling Reaction towards trans-THFs A brief overview of the acyloin coupling reaction is followed by description of the aim for this part of the project, using this process as a key step towards trans-THFs. Work directed towards the stereoselective protonation of the bis-enolate intermediate formed during the acyloin coupling is discussed. The exploitation of A1,3 strain was the most effective strategy found to control the diastereoselectivity in the protonation of the bis-enolate intermediate. Desymmetrisation Using Sharpless Asymmetric Epoxidation towards trans-THFs Strategy developed towards the synthesis of a 2,5-disubstituted 3-hydroxy trans-THF is studied. The optimisation of the synthesis of meso-hepta-1,6-diene-3,5-diol was examined and subsequent desymmetrisation using the Sharpless asymmetric epoxidation was explored. Approaches towards the FG Fragment of Pectenotoxin-4 The previous synthesis of the FG fragment was reviewed. Details of the retrosynthesis to be employed for the preparation of the southern hemisphere of pectenotoxin-4 are discussed. The desymmetrisation strategy previously explored was applied towards forming the F ring of pectenotoxin-4. The C31-40 carbon skeleton was successfully formed in 12 steps using a convergent synthesis. The elucidation of an X-ray crystal structure requires further exploration to confirm the relative and absolute configuration of the THF formed. Chapter 3: Experimental Full experimental procedures and characterisation of compounds are reported.
Supervisor: Donohoe, Timothy J. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Organic chemistry ; Organic synthesis ; trans-THFs ; Pectenotoxin-4