University of Sussex
Browse
Jiménez_Barrera,_Rosa_Martha.pdf (5.41 MB)

Studies towards the total synthesis of asteriscanolide

Download (5.41 MB)
thesis
posted on 2023-06-07, 15:56 authored by Rosa Martha Jiménez Barrera
The cyclooctane sesquiterpene lactone, asteriscanolide 1, has attracted considerable interest in the chemical literature since San Feliciano and colleagues first reported its isolation from Asteriscus aquaticus L. To date, no pharmaceutical applications have been found for 1. However, the challenge offered by the construction of its cyclooctanoid core represents an important target for the development of methods directed towards the preparation of other related eight-membered ring-containing terpenoids with more interesting biological properties. This thesis illustrates an investigation into the total synthesis of natural product asteriscanolide 1. Following up on the previous work established by Marsh,2 an approach to 1 was designed, seeking to build a suitable framework for an intramolecular [3 + 2] nitrile oxide-olefin cycloaddition (INOC) as the pivotal synthetic step to assemble the medium-sized ring. The INOC strategy was extensively investigated. As this remained unsuccessful, the investigation was extended to various other intramolecular strategies, including intramolecular [3 + 2] silyl nitronate-olefin cycloaddition (ISOC), samarium(II) iodide-mediated cyclisation, radical-mediated cyclisation, and nitronate anion-epoxide cyclisation, which identified certain limitations that would hinder further progress. To this end, a second generation towards 1 incorporating ring-closing metathesis (RCM) and intermolecular nitronate anion-epoxide addition was designed. A detail discussion of the results is contained within.

History

File Version

  • Published version

Pages

229.0

Department affiliated with

  • Chemistry Theses

Qualification level

  • doctoral

Qualification name

  • dphil

Language

  • eng

Institution

University of Sussex

Full text available

  • Yes

Legacy Posted Date

2011-06-20

Usage metrics

    University of Sussex (Theses)

    Categories

    No categories selected

    Exports

    RefWorks
    BibTeX
    Ref. manager
    Endnote
    DataCite
    NLM
    DC