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Use of camphor in terpenoid syntheses

University of British Columbia

Camphor has been functionalised at the C(5), C(6), C(8) and C(9) positions by procedures previously developed and the corresponding derivatives have subsequently been utilised as key intermediates in mono- and sesquiterpenoid syntheses. The monoterpenoid analogues of the plant growth-promotor (-)-cis-sativenediol and the growth-inhibitor (-)-helminthosporal, (-)-5-exo, 6-exo-dihydroxycamphene and (+)-1,4-diformyl-2,3,3-trimethylcyclopentene respectively, have been prepared from (-)-camphor by a synthetic route involving the 'remote oxidation' of (+)-isobornyl acetate to a mixture of 5- and 6-oxoisobornyl acetates. The trans-diol (-)-5-endo, 6-exo-dihydroxycamphene was also obtained during this study. The synthetic monoterpenoids and their enantiomers were found to be devoid of growth-promoting or growth-inhibiting properties on two varieties of rice (Oryza sativa). The 'remote oxidation' technique has also been applied to the synthesis of nojigiku alcohol [(+)-6-exo-hydroxycamphene], a metabolite of Chrysanthemum japonense, from (+)-camphor. The structure, absolute configuration, and physical constants of this monoterpenoid alcohol and its derivatives have thus been established. (+)-9-Bromocamphor was used as a starting material for two unsuccessful synthetic approaches to the trisnorsesquiterpenoid albene, a metabolite of plants of the genera Petasites albus (L.) Gearth and Adenostyles alliariae (G.) Kern. One of these routes was based on the proposal that epi-β- santalene, a natural sesquiterpenoid which had previously been synthesised in our laboratory, could be a biosynthetic precursor of albene. However, during these investigations the original structure of albene was revised and a third synthetic route to this compound using (+)-8-bromocamphor as starting material was therefore studied. (+)-8-Bromocamphor has also been utilised as the starting material in a synthetic approach to clausantalene, a sesquiterpenoid isolated from Clausena indica 0liv. (Rutaceae). A synthesis of dehydroclausantalene and epidehydroclausantalene T_9-hydroxy-9-(3' -methyl-V -butenyl )camphenes] has been accomplished but the regio- and stereoselective hydration of these two compounds to clausantalene and its epimer respectively is still under investigation.

Text

2010-03-20

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http://hdl.handle.net/2429/22209

Chemistry

University of British Columbia

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