Novel rearrangements of sesquiterpenoid panasinsane derivatives under acidic conditions.
The sesquiterpenoid panasinsane derivatives 11 and 14-16 have been prepared from caryophyllene oxide (7). The novel rearrangement reactions of compounds 11 and 14 under TCNE-catalyzed solvolysis conditions and the reactions of compounds 15 and 16 under superacid conditions (HSO3F/Et2O, -63 degrees C) have been investigated. The ginsenol derivative 17 is obtained from compounds 11 and 14 under TCNE-catalyzed conditions. The rearrangement of compounds 15 and 16 under superacid conditions leads to the novel sesquiterpene derivatives (1S,4S,7S,10S,11S)-3,3,10,11-tetramethyltricyclo[5.3.1.0(4,10)]undecan-1,11-yl sulfate (19) and (1S,4S,5S,8S)-2,2,4,8-tetramethyl tricyclo[3.3.2.1(4,8)]undecan-11-one (20). The influence of the secondary hydroxyl group at C-5 of the panasinsane derivatives on the course of these rearrangements is discussed.
Amigo
C F
CF
Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Cádiz, Apartado 40, 11510 Puerto Real, Cádiz, Spain.
Collado
I G
IG
Hanson
J R
JR
Hernández-Galán
R
R
Hitchcock
P B
PB
Macías-Sánchez
A J
AJ
Mobbs
D J
DJ
D006863:Hydrogen-Ion Concentration; D012717:Sesquiterpenes / Q000138:chemical synthesis* / Q000737:chemistry*; D013057:Spectrum Analysis
D012717:Sesquiterpenes; C431205:panasinsane