Synthesis of (+)-pechueloic acid and (+)-aciphyllene. Revision of the structure of (+)-aciphyllene

1αH,7αH,10αH-Guaia-4,11-dien-3-one and its 1βH,10βH diastereomer, easily obtained from (+)-dihydrocarvone, are good starting materials for the synthesis of natural guaiane derivatives. Allylic oxidation of the 1αH,10αH isomer gave as main product its 13-hydroxy derivative and a small amount of (+)-7β-hydroxy-1αH,10αH-guaia-4,11-dien-3-one, whereas the 1βH,10βH diastereomer afforded selectively the (−)-7α-hydroxy-1βH,10βH enantiomer in excellent yield. From the 13-hydroxy derivative (+)-pechueloic acid and (+)-methyl pechueloate were synthesized. Deoxygenation at C3 of the 1βH,10βH guaiadienone afforded a guaiadiene with the reported structure for aciphyllene but its spectral data did not agree with those reported for the natural diene. The structure of natural (+)-aciphyllene has been corrected to 1αH,7αH,10αH-guaia-4,11-diene obtained by deoxygenation of the 1αH,10αH guaiadienone.

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