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Thermal rearrangement of bicyclogermacrane-1,8-dione. Synthesis of humulenedione and (−)-cubenol, starting from natural (+)-Aromadendrene-V

✍ Scribed by Harrie J.M. Gijsen; Joannes B.P.A. Wijnberg; Aede de Groot


Book ID
104203083
Publisher
Elsevier Science
Year
1994
Tongue
French
Weight
800 KB
Volume
50
Category
Article
ISSN
0040-4020

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✦ Synopsis


Treatment of a distillation tail of Eucalyptus globulus, containing mainly (+)-aromadendrene (1) and (-)-alloaromadendrene (Z), with K/Al203 gives a quantitative conversion of 1 anti 2 into isoledene (4). Oxidative cleavage of the central double bond in 4 produces (+)-bicyclogermacrane-l,Sdione (5). Thermal rearrangement of 5 gives via a homo [1,5J hydrogen shift at relatively low

temperature the humulenedione 6, and at higher temperature (FVPJ the products 9 and 10 both with a cadinane skeleton. The naturally occurring humulenedione ( 7) and I-)-cubenol ( 17) can be synthesized starting from 6 and 9, respectively.