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.
| Identifer | oai:union.ndltd.org:ADTP/276036 |
| Date | January 1971 |
| Creators | Fullerton, T. J., 1947- |
| Publisher | ResearchSpace@Auckland |
| Source Sets | Australiasian Digital Theses Program |
| Language | English |
| Detected Language | English |
| Rights | Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated., http://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm, Copyright: The author |
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