Reactions of Diels-Alder adducts of a sugar-derived dihydropyranone leading to fused polycyclic compounds.
Manipulation of the ketone and alkene functions of cycloadducts 2, 3, and 4, derived from optically active (ee >86%) (S)-2-benzyl-2H-pyran-3(6H)-one (1), led to polycyclic systems having three or four fused rings. Reduction of the carbonyl group of the butadiene adduct (2) took place with low facial selectivity affording the alcohols 5 and 6 in 1:1.4 ratio. In contrast, a higher diastereoselection was observed for the reduction of the carbonyl of the cyclopentadiene adducts 3 and 4 to give the endo alcohols 10 and 13, respectively. The epoxidation of 6 showed low facial selectivity in the formation 7 and 8, whereas epoxidation of 10 and 13 took place from the exo face of the norbornene system to give spontaneously the polycyclic alcohols 11 and 14 by opening of the epoxide by intramolecular attack of the hydroxyl group of the pyranoid ring. Similarly, addition of iodine to 10 led to the polycyclic iodide 12.
Iriarte Capaccio
Christian A
CA
CIHIDECAR-CONICET, Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, 1428 Buenos Aires, Argentina.
Varela
Oscar
O
D000438:Alcohols / Q000737:chemistry; D001671:Biochemistry / Q000379:methods*; D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D002244:Carbon / Q000737:chemistry; D002845:Chromatography; D002855:Chromatography, Thin Layer; D003517:Cyclopentanes; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008969:Molecular Sequence Data; D010100:Oxygen / Q000378:metabolism; D011083:Polycyclic Compounds / Q000737:chemistry*; D013053:Spectrophotometry; D013237:Stereoisomerism; D014466:Ultraviolet Rays
D000438:Alcohols; D003517:Cyclopentanes; D011083:Polycyclic Compounds; D002244:Carbon; D010100:Oxygen