| Structure Identification: |
| Chem Pharm Bull (Tokyo). 2008 Mar;56(3):398-403. | | Concise syntheses of coronarin A, coronarin E, austrochaparol and pacovatinin A.[Pubmed: 18310958] | Total syntheses of (+)-coronarin A (1), (+)-Coronarin E (2), (+)-austrochaparol (3) and (+)-pacovatinin A (4) were achieved from the synthetic (+)-albicanyl acetate (6).
METHODS AND RESULTS:
Dess-Martin oxidation of (+)-albicanol (5) derived from the chemoenzymatic product (6) gave an aldehyde (7), which was subjected to Julia one-pot olefination using beta-furylmethyl-heteroaromatic sulfones (8 or 9 ) gave (+)-trans Coronarin E (2) and (+)-cis Coronarin E (12) with high cis-selectivity. The synthesis of (+)-coronarin A (1) from (+)-trans Coronarin E (2) was achiev-ed, while (+)-cis Coronarin E (12) was converted to the natural products (+)-(5S,9S,10S)-15,16-epoxy-8(17),13(16),14-labdatriene (13) and (+)-austrochaparol (3).
CONCLUSIONS:
By the asymmetric synthesis of (+)-3, the absolute structure of (+)-3 was determined to be 5S, 7R, 9R, 10S configurations. Homologation of (+)-albicanol (5) followed by allylic oxidation gave (7 alpha)-hydroxy nitrile (17), which was finally converted to the natural (+)-pacovatinin A (4) in 8 steps from (+)-albicanol (5).
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