Stereospecific Syntheses from Podocarpic Acid

The triterpene precursor, 12-methoxypodocarpa-8,11,13-trien-3-one (46)*, has been prepared via the 3a-alcohol (48) formed by opening of the 3a,4a-epoxide (13) with lithium diethylamide. The total synthesis of the methyl ether of the natural product, (+)-hinokione, has been achieved by a similar sequence involving prior addition of an isopropyl group at C 13 of the methoxy acid (4) ( Scheme 1 ) . A study of the boron trifluoride rearrangements of the three epoxides (12), (13), and (14), has been made using benzene and dimethyl sulphoxide as solvents. The stereochemistry of a series of 6-bromo-7-oxo derivatives of diterpenoids possessing an aromatic ring-C is discussed and the assignment of configuration of the 6-bromo substituents from n.m.r. and n.0.e. data is examined. A preliminary investigation into the possibility of preparing a 9a-methyl steroidal analogue by addition of a cyclopentatone ring across positions 3 and 4 of ring-A of the podocarpic system is also reported.

Name thesis:degree_name

PhD

Level thesis:degree_level

Doctoral

Discipline thesis:degree_discipline

Chemical Sciences

Grantor dc:publisher

ResearchSpace@Auckland

Year dc:date.issued

1971

Author dc:creator

• Fullerton, T. J., 1947-

Advisor dc:contributor.advisor

• Drs J.M. Coxon and M.P. Hartshorn

Statement dc:rights

• Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

Licence dc:rights.uri

• https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm

Language dc:language.iso

en

Handle dc:identifier.uri

https://hdl.handle.net/2292/2097

OAI identifier oai:identifier

oai:researchspace.auckland.ac.nz:2292/2097