dc.contributor.advisor |
Woodgate, Paul |
en |
dc.contributor.author |
Higgs, Paul Ian |
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dc.date.accessioned |
2007-07-31T06:10:26Z |
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dc.date.available |
2007-07-31T06:10:26Z |
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dc.date.issued |
1993 |
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dc.identifier |
THESIS 93-284 |
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dc.identifier.citation |
Thesis (PhD--Chemistry)--University of Auckland, 1993 |
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dc.identifier.uri |
http://hdl.handle.net/2292/1195 |
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dc.description |
Full text is available to authenticated members of The University of Auckland only. |
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dc.description.abstract |
Six-membered carbocyclic or five-membered heterocyclic rings were annulated onto ring-C of the podocarpane skeleton by trapping a diterpenoid aryne with cyclic dienes and l,3-dipolar species. The [4+2] epoxy adducts were converted regiospecifically into previously unavailable chrysen-4-ols.
The anthranilic acid used to generate aryne at C 13 by nitrite treatment, was synthesised from the 14-amino compound. The latter was generated regiospecifically and in excellent yield via the same aryne by treatment of the 13-bromo compound with sodamide in liquid ammonia The amine was converted into the anthranilic acid by two separate synthetic routes; firstly by directed lithiation and trapping of the lithium species with a CO2 moiety, and secondly via oxidative cleavage of an isatin generated across positions 13 and 14.
Attempts to convert the 14-amine into a 1-aminotriazole, an alternative aryne precursor, were unsuccessful. However this led to a new novel heterocyclic phenanthropyrazole ring system in high yield.
In an unrelated project a novel procedure was developed for the regioselective hydroxylation of ring-C aromatic diterpenoids via their (η6-arene)tricarbonylchromium(0) complexes. Lithiation/cupration/oxidation gave high yields from methoxyarene complexes with an unhindered ortho position. |
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dc.language.iso |
en |
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dc.publisher |
ResearchSpace@Auckland |
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dc.relation.ispartof |
PhD Thesis - University of Auckland |
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dc.relation.isreferencedby |
UoA9951897214002091 |
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dc.rights |
Restricted Item. Available to authenticated members of The University of Auckland. |
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dc.rights |
Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated. |
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dc.rights.uri |
https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm |
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dc.title |
Annulations of podocarpic acid derivatives via aryne intermediates |
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dc.type |
Thesis |
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thesis.degree.discipline |
Chemistry |
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thesis.degree.grantor |
The University of Auckland |
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thesis.degree.level |
Doctoral |
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thesis.degree.name |
PhD |
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dc.rights.holder |
Copyright: The author |
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