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Title: Synthesis of decanolides and deoxysugars
Author: Hornsby, Thomas W.
ISNI:       0000 0004 6059 3848
Awarding Body: University of Bristol
Current Institution: University of Bristol
Date of Award: 2016
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This thesis describes investigations of the synthesis and biomimetic rearrangements of cephalosporolide B 8 and the further development of novel Prins methodology for the synthesis of deoxysugars and analogues. A variety of synthetic routes to 'cephalosporolide B were investigated (chapters 2 & 3), the key steps in the final route were the oxidative lactonisation of 1,6-diol 249 to lactone 271, and· subsequent deprotection/translactonisation to give the decanolide core. The biomimetic reaction of protected cephalosporolide B 8 with 4-methyl-6-hydroxy- 2-pyrone was investigated, giving hemiketal 273. In light of this, a new biosynthetic pathway has been proposed, in which the open chain precursor of cephalosporolide B is implicated in the formation of tenuipyrone 7. Chapter 4 describes the synthesis of glycosyl donor 338 using the Prins cyclisation of novel silyl acetal 330 with homoallylic alcohol 345, followed. by a Tamao-Fleming oxidation and acetylation. Diacetate 338 undergoes a simple glycosylation reaction with cyc1ohexanol. The scope of an alternative Prins cyc1isation using a-silyl homoallylic alcohol 357 was investigated. By varying the cyc1isation conditions both alcohols and acetates were installed at C-3. Using different aldehydes allows the introduction of different groups at C-S.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available