1 海洋産チアゾール含有ポリケチド,マイコチアゾールの合成研究(口頭発表の部)
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Mycothiazole (1) was isolated from Spongia mycofijiensis collected from Vanuatu by Crews et al. and it exhibited anthelmintic activity (in vitro) while high toxicity was observed in mice. The most unique feature of this structure is a thiazole ring which is imbedded between two acyclic polyketide chains. Furthermore the side chains contain nonconjugated and conjugated diene systems. Although 1 has only one stereogenic center on the secondary alcohol, its absolute configuration has been unknown. According to our synthetic strategy, we started to synthesize the left fragment (3) which contains a thiazole ring and a nonconjugated diene system. In order to synthesize a thiazole ring, we attempted the Hantzch method via the thioamide 8. While this procedure was unsuccessful, the thiazole moiety 12 could be obtained by our method, CMD (Chemical Manganese Dioxide) oxidation procedure from the corresponding thiazolidine 11 in one step. In this oxidation, activation of CMD by azeotropic dehydration with benzene was needed to prevent hydrolysis of 11. The skipped diene was constructed by using the Stine cross coupling two times. The coupling of 15 with the tin compound 18 gave 19 in good yield, and the bromination of the primary alcohol in 19 followed by coupling with vinyl tributyltin furnished the nonconjugated diene. As part of synthesis of the right fragment (3), the addition of hydrogen iodine to the alkyne 21 gave the vinyl iodide 22, which was coupled with propargyl alcohol by the Sonogashira coupling to give 23. However, the attempt of semi-hydrogenation of the alkyne which conjugated with exo-olefin failed. Thus we changed the plan that the exo-olefin would be introduced by the Wittig type reaction. The Nozaki-Hiyama-Kishi coupling of the vinyl iodide 29 with the aldehyde 31 gave 32, and the oxidation of the allyl alcohol in 32 afforded the α,β-unsaturated ketone 33. Construction of exo-methylene and further synthetic studies toward total synthesis of mycothiazole (1) are actively in progress.
- 天然有機化合物討論会の論文
- 1999-09-01
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