23 海産抗腫瘍性マクロリド、アプリロニンAの立体化学と合成研究(口頭発表の部)

DOI

書誌事項

タイトル別名
  • 23 STEREOCHEMISTRY AND SYNTHETIC STUDY OF APLYRONINE A, AN ANTITUMOR MACROLIDE OF MARINE ORIGIN

抄録

Aplyronine A (1) is a potent antitumor macrolide isolated as a minute component from the sea hare Aplysia kurodai. The gross structure of 1 was determined by the spectral analysis and chemical degradation. We report herein the absolute stereostructure of 1 and the result of the synthetic study. Chemical degradation of 1 afforded five fragments 2-6. Enantioselective syntheses of the fragments 4a and 5a were performed to disclose the absolute stereochemistry of seven chiral centers (C7-C10, C13, C17, and C19). HPLC analyses of the fragments 2 and 3 using chiral columns disclosed that N,N,O-trimethylserine and N,N-dimethylalanine moieties of 1 were scalemic mixtures (S:R=52:48 for 2; 72:28 for 3). On the basis of the result of the previous and present studies, the absolute stereostructure of aplyronine A (1) was elucidated unambiguously. The synthetic study of 1 was carried out using the Evans aldol reaction and the Sharpless epoxidation reaction as key steps. Starting from N-propionylurethane 11, the C5-C20 segment 13 and the C21-C34 segment 16 were synthesized. The Julia coupling reaction of 13 with 16 followed by four-carbons homologation and lactonization provided 24-membered lactone 17.

収録刊行物

詳細情報 詳細情報について

  • CRID
    1390001206077602176
  • NII論文ID
    110006679187
  • DOI
    10.24496/tennenyuki.35.0_174
  • ISSN
    24331856
  • 本文言語コード
    ja
  • データソース種別
    • JaLC
    • CiNii Articles
  • 抄録ライセンスフラグ
    使用不可

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