Total synthesis of the proposed structure of sclerophytin F and structure re-evaluation

Delion, Laëtitia (2014) Total synthesis of the proposed structure of sclerophytin F and structure re-evaluation. PhD thesis, University of Glasgow.

Abstract

The thesis presents the first enantioselective synthesis of the proposed structure of sclerophytin F and consequently, the first total synthesis of a cladiellin family member having the S-configuration at the C-3 stereocentre. Three novel enantioselective routes are described to access a pivotal intermediate; then, the synthesis follows three key steps: i) radical-mediated cyclisation, ii) oxonium ylide formation and [2,3]-sigmatropic rearrangement, iii) Diels-Alder cycloaddition to deliver the core of the natural product. The novelty of the route relies on the introduction of the C-3 methyl group at an early stage of the synthesis. As anticipated, the presence of this extra methyl had significant influence on many transformations. Finally, the elaboration of the core to meet the proposed structure was completed. Unfortunately, none of the recorded data matched those originally reported for the natural compound. A further three stereoisomers were synthesised but their data also did not match the original.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Sclerophytin, natural product, total synthesis, structure elucidation
• Subjects: Q Science > QD Chemistry
• Colleges/Schools: College of Science and Engineering > School of Chemistry
• Supervisor's Name: Clark, Professor J. Stephen
• Date of Award: 2014
• Depositing User: Miss Laëtitia Delion
• Unique ID: glathesis:2014-5926
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 20 Jan 2015 15:01
• Last Modified: 22 Jan 2015 16:09
• URI: https://theses.gla.ac.uk/id/eprint/5926