In connection with synthetic study of lycophlegmarine, stereoselective synthesis of the allyl alcohol (D : R=CF
3), which was an intermediate of fawcettimine synthesis, was investigated. In that occasion, acylation of 1 and 2 in pyridine with (CF
3CO)
2O overnight gave mainly the unexpected epoxide (5) and (6), respectively. Acylation with pyridine-(CF
3CO)
2O under oxygen atmosphere gave only the epoxide for 3 h, and acylation with NEt
3-(CF
3CO)
2O or pyridine-Ac
2O afforded the corresponding diacyl olefin even under oxygen atmosphere. Moreover, epoxides (5) and (6) were converted to the allyl alcohol (D : R=CF
3) in a high yield via the same ketone (B=10). This means that stereoselective and formal synthesis of fawcettimine was achieved.
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