77 マイカラミドAおよび関連化合物の合成研究(ポスター発表の部)

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概要

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• Mycalamide A (1), isolated from a New Zealand sponge of the genus Mycale, exhibits potent antiviral and antitumor activities. The structure of 1 is strikingly similar to that of pederin (3), a strong insect poison. Recently, Kishi has accomplished the first total synthesis of 1 via the coupling of the left half 6 and the right half 7; the right half 7 was synthesized starting from methyl α-D-glucopyranoside and the left half 6 was prepared in two steps from one of the intermediates in our total synthesis of pederin (3). We now report our recent studies of the synthesis of Mycalamide A (1). 1) Synthesis of 14 starting from (S)-malic acid Ketone 10, prepared from (S)-malic acid, was reduced with L-Selectride to give β-alcohol 11 stereoselectively. Treatment of 11 with 1,2-ethanedithiol-BF_3・Et_2O followed by acetonization produced δ-lactone 12, which was converted into enone 14 in four steps; 1) DIBAH, 2) CH(OMe)_3/CSA, 3) NBS, 4) Bu_4NF. 2) Synthesis of 14 starting from (R)- or (S)-pantolactone An alternative route for the synthesis of 14 was developed starting from (R)- or (S)-pantolactone as follows. Epoxide 16 prepared from pantolactone was converted into 19 in four steps; 1) AllylMgCl/CuI, 2) OsO_4/NMO, 3) NaIO_4, 4) MsCl/Et_3N/i-Pr_2NEt. MCPBA oxidation of 19 followed by LiAlH_4 reduction produced syn-triol 21 stereoselectively. 21 was also prepared from 16 in 2 steps via dihydroxylation of 23 with OsO_4-NMO (syn-21:anti-24=1:1.2). syn-Triol 21 was converted into enone 14 via 27. 3) Synthesis of right half 7 from 14 Reduction of enone 14 with NaBH_4-CeCl_3 gave only α-alcohol 29 which was treated with MeI-KH to give 31. MCPBA oxidation of 31 followed by hydrolysis and acetylation produced diacetate 33. Treatment of 33 with propargyltrimethylsilane-TMSOTf afforded β-allene 44 stereoselectively. 44 was converted into 46 in four steps; 1) K_2CO_3, 2) Im_2CO, 3) O_3, 4) (CH_2O)n/HCl. Acetylation of 46 followed by treatment with TMSN_3-TMSOTf gave azide 48. The ^1H-NMR data of the synthetic 48 were identical with those of Kishi's intermediate, which was hydrogenated to give the right half 7. Syntheses of mycalamide A (1) and the related compounds are now in progress.

• 天然有機化合物討論会の論文
• 1993-09-10

著者

• 松倉 弘子

  理研

• 中田 忠

  理研

• 大石 武

  理研

• 大石 武

  Faculty Of Engineering Yokohama National University:(present Address)meiji College Of Pharmacy

• 大石 武

  理研:(現)明治薬科大学

• 中田 忠

  東京理大・理

• 蹇 敦龍

  理研

• Qais N.

  理研

• 長島 弘秋

  理研

• 中川 忠清

  理研

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