Thesis

Unique approaches towards the synthesis of polycyclic sesquiterpene targets

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Awarding institution
  • University of Strathclyde
Date of award
  • 2014
Thesis identifier
  • T13794
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Department, School or Faculty
Abstract
  • A programme of work towards the total synthesis of the natural product sesquithuriferone has been performed, with significant advances towards the realisation of this overall goal achieved. From this perspective, two main synthetic strategies have been investigated towards the synthesis of a common early-stage intermediate, critical to the construction of the core tricyclic scaffold. In this regard, both of these preparative pathways were explored simultaneously, with the aim of developing a robust and versatile route through to the natural product target. The first of these approaches involved the development of a novel [3+3]-sigmatropic rearrangement, to provide access to range of substituted cyclopentanones. Towards this aim, significant progress has been achieved, with late stage compounds having been prepared. Initial studies concentrated specifically on the synthesis of a novel ε-lactone key to the synthesis of sesquithuriferone. Additionally, a novel strategy to access a range of substituted systems of structural similarity has been developed and, within the body of this research, a number of preparative pathways designed to access these systems have been explored. As each of the individual routes have been investigated, short optimisation studies have been pursued. The second route towards the synthesis of the common intermediate involved an umpolung conjugate addition strategy. Towards this aim, a robust and versatile set of protocols have been developed to provide access to both the racemic and asymmetric variants of this compound. Towards the construction of the key tricyclic core of sesquithuriferone, a Pauson-Khand approach was pursued. In this regard, a wide range of structural derivatives were synthesised and examined, under a spectrum of standard protocols, to identify an optimal structure to facilitate this key organometallic annulation. Upon completion of this optimisation programme, a range of synthetic strategies were explored towards the completion of the desired natural target. Significant progress towards this goal has been achieved, with the preparation of several late stage compounds completed. In addition, through the development of this route towards sesquithuriferone, several points of diversity have been identified and investigated with the aim of assessing if the identified synthetic strategy under investigation could be applicable to the synthesis of other members of the same family of natural compounds.
Resource Type
DOI
Date Created
  • 2013
Former identifier
  • 1036787

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