dc.contributor.advisor |
Harvey, Joanne E. |
|
dc.contributor.advisor |
Teesdale-Spittle, Paul |
|
dc.contributor.author |
Somarathne, R.M. Kalpani K. |
|
dc.date.accessioned |
2014-11-23T23:32:16Z |
|
dc.date.accessioned |
2022-11-03T02:16:52Z |
|
dc.date.available |
2014-11-23T23:32:16Z |
|
dc.date.available |
2022-11-03T02:16:52Z |
|
dc.date.copyright |
2014 |
|
dc.date.issued |
2014 |
|
dc.identifier.uri |
https://ir.wgtn.ac.nz/handle/123456789/29614 |
|
dc.description.abstract |
Carbohydrate-derived cyclopropanes combine both the stereochemical wealth of carbohydrates and the reactivity of cyclopropanes. A diverse variety of reaction modes for these cyclopropyl carbohydrates can be harnessed for the synthesis of natural products and other targets.
The natural products (−)-TAN-2483A and (−)-TAN-2483B are fungal secondary metabolites displaying a variety of bioactivities such as inhibition of c-src kinase action and parathyroid hormone-induced bone resorption. This thesis described several synthetic approaches to the natural product (−)-TAN-2483B and analogues of (−)-TAN-2483B employing cyclopropane ring expansion.
The synthetic route to (−)-TAN-2483B began with the readily available substrate D-mannose. The pyran ring unsaturation of the natural product was established by a cyclopropanation-ring expansion sequence. A synthetic strategy via dichlorocyclopropane-based intermediates is described in chapter 2. This being unsuccessful, an alternative approach via 2-fomyl-glycal was developed in chapter 3. The chapter 2 and 3 provided a solid background for the achievement of the analogues synthesis illustrated in chapter 4 via dibromocyclopropane. Lewis acid-mediated alkynylation followed by Pdcatalysed carbonylative lactonisation was successfully utilised in the revelation of the furo[3,4-b]pyran ring skeleton. This route afforded analogues of TAN-2483B; the Z-and E-unsaturated ethyl esters 140 and 141 and hydroxy(−)-TAN-2483B 145. The total synthesis of (−)-TAN-2483B was not achieved due to unforeseen obstacles encountered in the deoxygenation of the side arm of 335 (Chapter 4) into the E-propenyl side arm of (−)-TAN-2483B. |
en_NZ |
dc.language.iso |
en_NZ |
|
dc.publisher |
Te Herenga Waka—Victoria University of Wellington |
en_NZ |
dc.rights |
Access is restricted to staff and students only until 12/2016. For information please contact the library. |
en_NZ |
dc.subject |
TAN-2483B |
en_NZ |
dc.subject |
Cyclopropane |
en_NZ |
dc.subject |
Carbonylation |
en_NZ |
dc.title |
Synthesis of Highly Functionalised Furo[3,4-b]pyrans: Towards the Fungal Metabolite (−)-TAN-2483B |
en_NZ |
dc.type |
Text |
en_NZ |
vuwschema.contributor.unit |
School of Chemical and Physical Sciences |
en_NZ |
vuwschema.subject.anzsrcfor |
030401 Biologically Active Molecules |
en_NZ |
vuwschema.subject.anzsrcfor |
030502 Natural Products Chemistry |
en_NZ |
vuwschema.subject.anzsrcfor |
030503 Organic Chemical Synthesis |
en_NZ |
vuwschema.subject.anzsrcseo |
970103 Expanding Knowledge in the Chemical Sciences |
en_NZ |
vuwschema.type.vuw |
Awarded Doctoral Thesis |
en_NZ |
thesis.degree.discipline |
Chemistry |
en_NZ |
thesis.degree.grantor |
Te Herenga Waka—Victoria University of Wellington |
en_NZ |
thesis.degree.level |
Doctoral |
en_NZ |
thesis.degree.name |
Doctor of Philosophy |
en_NZ |