Stereoselective synthesis of (+)-11betaH,13-dihydroestafiatin, (+)-11betaH,13-dihydroludartin, (-)-compressanolide, and (-)-11betaH,13-dihydromicheliolide from santonin.
Starting from 2 and 3, obtained from santonin (1), we have synthesized natural guaianolides 4-7. Chemoselective epoxidation of 2 gave (+)-11betaH,13-dihydroestafiatin (4), and epoxidation of 3 followed by regioselective elimination of the hydroxyl group afforded (+)-11betaH,13-dihydroludartin (5). Sharpless' mild regioselective ring-opening of 4 and 5 followed by hydrogenolysis yielded (-)-compressanolide (6) and (-)-11betaH,13-dihydromicheliolide (7), respectively.
Bargues
Victoria
V
Departamento de Química Orgánica, Facultad de Química, Universitat de Valencia, E-46100 Burjassot, Valencia, Spain.
Blay
Gonzalo
G
Cardona
Luz
L
García
Begoña
B
Pedro
José R
JR
D002384:Catalysis; D003500:Cyclization; D007783:Lactones / Q000138:chemical synthesis*; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D012500:Santonin / Q000031:analogs & derivatives / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
C471679:11,13-dihydroestafiatin; C471678:11,13-dihydroludartin; C471677:11,13-dihydromicheliolide; D007783:Lactones; C471676:compressanolide; D012500:Santonin