Investigations of the type ii intramolecular Diels-Alder reaction directed toward natural product synthesis

Simple item page
dc.contributor.authorMuscroft-Taylor, Andrew Cliveen
dc.date.accessioned2008-09-07T23:19:31Z
dc.date.available2008-09-07T23:19:31Z
dc.date.issued2006en
dc.description.abstractThis thesis describes synthetic studies directed towards the total synthesis of the nakafuran and florlide marine natural products. Chapter One provides an overview of the importance of natural products to current medicinal chemistry and describes how the "supply issue" associated with these biologically derived compounds can be resolved through the process of total synthesis. Two families of marine natural products, the nakafurans and the florlides, are introduced as synthetic targets and strategies utilising a type II intramolecular Diels-Alder (IMDA) reaction to achieve their total synthesis are delineated. The efficient preparation of regio- and stereodefined vinyl coupling fragments via hydrostannylation and hydrohalogenation methodology is described in Chapter Two. The palladium-catalysed cross-coupling of these fragments, via Stille or Negishi coupling methodology, yielded dienes which were successfully advanced to IMDA triene precursors. Chapter Three describes investigation of the type II IMDA reaction to give bicyclo[4.3.1]decene carbocyclic skeletons. A facile acid-catalysed 6,7-alkene to 7,8-alkene olefinic isomerisation, via a proposed oxonium intermediate, and the inability to appropriately functionalise the desired adducts impeded progress along the synthetic route. Molecular modelling was conducted to investigate the causes of this unexpected reactivity. Investigations in Chapter Four describe the successful synthesis and cyclisation of homomethyl triene analogues prepared via application of enyne metathesis chemistry. The use of an exo-cyclopropylcarbinyl fragmentation was found to be unsuccessful as a means of installing the desired 6-methyl-bicyclo[4.3.1]decan-2-one core with a competing endo-ring expansion giving rise to a bicyclo[4.4.1]undecane ring system. Chapter 5 summarises the above results and gives a brief discussion of the future potential of this research to provide for a total synthesis of the nakafuran and florlide natural products.en
dc.identifier.urihttp://hdl.handle.net/10092/1290
dc.identifier.urihttp://dx.doi.org/10.26021/6903
dc.language.isoen
dc.publisherUniversity of Canterbury. Chemistryen
dc.relation.isreferencedbyNZCUen
dc.rightsCopyright Andrew Clive Muscroft-Tayloren
dc.rights.urihttps://canterbury.libguides.com/rights/thesesen
dc.subjectType II Intramolecular Diels-Alder reactionen
dc.subjectIMDAen
dc.subjectT2IMDAen
dc.subjecttransition metal-catalysed cross-couplingen
dc.subjectStilleen
dc.subjectNegishien
dc.subjectHydrostannylationen
dc.subjectEnyne metathesisen
dc.subjectRadical Fragmentationen
dc.subjectNatural product synthesisen
dc.subjectNakafuranen
dc.subjectXenolideen
dc.subjectFlorlideen
dc.subjectBicyclo[4.3.1]decaneen
dc.subjectBicyclo[4.3.1]decanoneen
dc.subjectBicyclo[5.3.1]undecanoneen
dc.titleInvestigations of the type ii intramolecular Diels-Alder reaction directed toward natural product synthesisen
dc.typeTheses / Dissertations
thesis.degree.disciplineChemistryen
thesis.degree.grantorUniversity of Canterburyen
thesis.degree.levelDoctoralen
thesis.degree.nameDoctor of Philosophyen
uc.bibnumber1022092en
Files
Original bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
thesis_fulltext.pdf
Size:
2.06 MB
Format:
Adobe Portable Document Format
Download
Collections
Science: Theses and Dissertations