Syntheses of (+)-alismoxide and (+)-4-epi-alismoxide.
The first total syntheses of (+)-alismoxide and (+)-4-epi-alismoxide are reported. Formal chemo-, regio-, and stereoselective addition of water to 10alpha-acetoxy-1alphaH,5betaH-guaia-3,6-diene afforded the target compounds after reduction. The absolute stereochemistry of (+)-alismoxide has been established. The low [alpha](D) +8.6 value indicates that significant amounts of alismoxide result from biosynthetic processes. Furthermore, the structure of the natural guaienediol isolated from Silphium perfoliatum has been corrected to (-)-alismoxide.
Blay
Gonzalo
G
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, E-46100, Burjassot, València, Spain.
García
Begoña
B
Molina
Eva
E
Pedro
José R
JR
D019659:Asteraceae / Q000737:chemistry; D052176:Azulenes / Q000737:chemistry*; D006147:Guanine / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure; D045789:Sesquiterpenes, Guaiane / Q000737:chemistry*; D013237:Stereoisomerism; D014867:Water / Q000737:chemistry
D052176:Azulenes; D045789:Sesquiterpenes, Guaiane; C521316:alismoxide; D014867:Water; D006147:Guanine; C019408:guaiene