2017年7月
Total Syntheses of Lepadiformine Marine Alkaloids with Enantiodivergency, Utilizing Hg(OTf)(2)-Catalyzed Cycloisomerization Reaction and their Cytotoxic Activities
CHEMISTRY-A EUROPEAN JOURNAL
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- 巻
- 23
- 号
- 40
- 開始ページ
- 9535
- 終了ページ
- 9545
- 記述言語
- 英語
- 掲載種別
- 研究論文(学術雑誌)
- DOI
- 10.1002/chem.201701475
- 出版者・発行元
- WILEY-V C H VERLAG GMBH
The enantioselective total syntheses of lepadiformine marine alkaloids, azatricyclic natural products isolated from marine tunicates, were completed. These alkaloids have a unique chemical structure characterized by the trans-1- azadecalin (AB ring system) fused with the spirocyclic ring (AC ring system). Here we found that a cycloisomerization reaction from functionalized linear substrates to a 1-azaspiro[ 4.5] decane framework corresponding to the AC ring in lepadiformines is promoted by a catalytic amount of mercury(II) triflate (Hg(OTf)(2)). The total syntheses of (-)-lepadiformine-s A and B were achieved in 28% and 21% overall yields, respectively, through the novel cycloisomerization reaction. The syntheses of (+)-and (-)-lepadiformine C hydrochloride salts also enabled us to determine the absolute configuration of natural lepadiformine C. It has been found that a phenomenon of enantiodivergence occurs in lepadiformine alkaloids from a single species of marine tunicate, Clavelina moluccensis. The cytotoxic activities of synthesized lepadiformine hydrochloride salts and their synthetic intermediates were evaluated.
- リンク情報
- ID情報
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- DOI : 10.1002/chem.201701475
- ISSN : 0947-6539
- eISSN : 1521-3765
- Web of Science ID : WOS:000405695400016