24 海洋産ポリエーテルマクロリド、ハリコンドリンBの全合成研究(口頭発表の部)

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概要

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• Halichondrins are marine natural products isolated from Halichondria okadai Kadota in low yield. Halichondrin B (1) is a representative member and exhibits remarkably powerful antitumor activity in vitro and in vivo. Additionally, 1 is a considerably complex molecule containing 32 asymmetric carbons, substituted tetrahydrofuran and pyran and spiroketal rings, and a large membered lactone. During course of some synthetic studies of 1, Kishi's group succeeded in the first total synthesis of 1 in 1992. For the purpose of establishing a stereoselective and efficient synthetic pathway of 1, we begun to synthesize 1 in 1989. We report here a stereocontrolled synthesis of four fragments, 2,3,5 and 6. As our synthetic program was illustrated in scheme 1, halichondrin B (1) was expected to be synthesized from four convenient fragments, C_1-C_<15> (2), C_<16>-C_<26> (3), C_<27>-C_<36> (5) and C_<37>-C_<54> (6). Tricyclic compound (18a) corresponding to C_1-C_<13> part was stereoselectively synthesized from D-glucose. The C_<16>-C_<26> fragment (3) was also stereoselectively prepared from D-malic acid. Two fragments (5,6) were stereoselectively synthesized from dimethyl L-tartrate as a common starting material. Coupling between the lithium enolate of 3, generated by treatment with LDA, and the aldehyde (5) proceeded smoothly and stereoselectively to afford the β-hydroxy ester (41) as a sole product. Construction of E ring was achieved by treatment with BF_3・OEt_2 in the presence of Et_3SiH in CH_2Cl_2. Other coupling programs toward the total synthesis of 1 is now in progress.

• 天然有機化合物討論会の論文
• 1993-09-10

著者

• 米光 宰

  岡山理大理

• 米光 宰

  Faculty of Pharmaceutical Sciences, Hokkaido University

• 米光 宰

  北大薬

• 米光 宰

  Faculty Of Pharmaceutical Sciences Hokkaido University

• 堀田 清

  北大薬

• 長澤 正明

  北大薬

• 八谷 俊一郎

  北大薬

• 荻原 和仁

  北大薬

• 櫻井 庸二

  Faculty of Pharmaceutical Sciences, Hokkaido University

• 八谷 俊一郎

  Faculty of Pharmaceutical Sciences, Hokkaido University

• 長澤 正明

  Faculty of Pharmaceutical Sciences, Hokkaido University

• 櫻井 庸二

  北大薬

• 彦田 匡毅

  北大薬

• 前野 恭一

  北大薬

• 八谷 俊一郎

  Faculty Of Pharmaceutical Sciences Hokkaido University

• 堀田 清

  Faculty Of Pharmaceutical Sciences Health Science University Of Hokkaido

• 櫻井 庸二

  Faculty Of Pharmaceutical Sciences Hokkaido University

• 長澤 正明

  Faculty Of Pharmaceutical Sciences Hokkaido University

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