Annulations of podocarpic acid derivatives via aryne intermediates

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dc.contributor.advisor Woodgate, Paul en Higgs, Paul Ian en 2007-07-31T06:10:26Z en 2007-07-31T06:10:26Z en 1993 en
dc.identifier THESIS 93-284 en
dc.identifier.citation Thesis (PhD--Chemistry)--University of Auckland, 1993 en
dc.identifier.uri en
dc.description Full text is available to authenticated members of The University of Auckland only. en
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. en
dc.language.iso en en
dc.publisher ResearchSpace@Auckland en
dc.relation.ispartof PhD Thesis - University of Auckland en
dc.relation.isreferencedby UoA9951897214002091 en
dc.rights Restricted Item. Available to authenticated members of The University of Auckland. en
dc.rights Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated. en
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dc.title Annulations of podocarpic acid derivatives via aryne intermediates en
dc.type Thesis en Chemistry en The University of Auckland en Doctoral en PhD en
dc.rights.holder Copyright: The author en

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