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Title: Total synthesis of the callipeltoside aglycon and the synthesis of novel ring analogues of elaiophylin
Author: Davies, R. D. M.
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 2001
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Part I - The first part of this dissertation describes the first total synthesis of the callipeltoside aglycon. An expedient synthesis of alglycons 210 and 212 has been accomplished starting from aldehydes 79 and 80, β-keto ester 75, chiral ketone 77 and epichlorohydrin. Our synthesis exploits a recently developed vinylogous aldol reaction applied in tandem with our own diastereoselective boron aldol methodology. Both chiral cyclopropanes were synthesised in an enantiocontrolled manner via a directed Simmons-Smith cyclopropanation. Part II - The second part of this dissertation describes studies into the novel Stille cyclooligomerisation developed in work towards the total synthesis of elaiophylin. The macrocyclic precursors 246 and 308 were efficiently synthesised from chiral ketone 240, in 47% and 42% respectively (Scheme B). (Fig. 6783B) The cyclooligomerisation of the precursors 246 and 308 proceeded via a double copper-mediated cross-coupling reaction which generated a library of elaiophylin ring analogues of varying size. The influence of temperature and concentration on the overall yield and product distribution has been examined, indicating a predisposition of 246, biased towards trimer formation. Cyclisation of the TES protected precursor proceeded less efficiently, this time generating the dimeric product with marginal selectivity (Scheme C).
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available