Exploiting pseudo-symmetry in the synthesis of the I–M fragment of ciguatoxin CTX3C

Popadynec, Michael (2017) Exploiting pseudo-symmetry in the synthesis of the I–M fragment of ciguatoxin CTX3C. PhD thesis, University of Glasgow.

Due to Embargo and/or Third Party Copyright restrictions, this thesis is not available in this service.
Printed Thesis Information: https://eleanor.lib.gla.ac.uk/record=b3295396


Marine polycyclic ethers are natural products isolated from marine plankton dinoflagellates such as Gambierdiscus toxicus and Karenia breve. They possess characteristic flat, semi-rigid, ladder-like structures and represent some of the largest, and most toxic, non-polymeric natural products discovered to date. Seafood contaminated with minute quantities of polycyclic ethers causes ciguatera, a debilitating illness that has been reported to last for more than 20 years.

The first chapter of this thesis provides an introduction to marine polycyclic ethers, detailing their origins, biosynthesis and mechanism of action. Prior syntheses of members of the ciguatoxin family by Hirama, Isobe, Kadota and Fujiwara are reviewed, with focus on the cyclisation strategies employed by each group. The methodology and two-directional strategies developed by the Clark group are reviewed. Examples of the implementation of these strategies in the reported syntheses of the F–J fragment of the gambieric acids and the A–E fragment of CTX3C are provided.

The second chapter of the thesis concerns the construction of the I–M fragment of CTX3C. The two-directional strategy is implemented over several steps, including alkylation, ringclosing metathesis and diastereoselective allylation. The synthetic route from tri-O-acetal-Dglucal to the I–L tetracycle is described and this section concludes with a future outlook.

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Keywords: Ciguatoxin, CTX3C, polycyclic, ether, PCE, natural product, synthesis, ciguatera, total synthesis.
Subjects: Q Science > QD Chemistry
Colleges/Schools: College of Science and Engineering > School of Chemistry
Funder's Name: Engineering and Physical Sciences Research Council (EPSRC)
Supervisor's Name: Clark, Professor J. Stephen
Date of Award: 2017
Embargo Date: 20 December 2021
Depositing User: Mr. Michael Popadynec
Unique ID: glathesis:2017-8644
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 21 Dec 2017 10:44
Last Modified: 11 Aug 2022 09:09
Thesis DOI: 10.5525/gla.thesis.8644
URI: https://theses.gla.ac.uk/id/eprint/8644

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