100(P-57) スフェノロバン型ジテルペン三種の全合成と絶対配置 : オレフィンメタセシス反応を用いる三置換二重結合を含む七員環の効率的合成(ポスター発表の部)
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Compounds 1 and 2 were isolated from the liverwort Anastrophyllum auritum. Tormesol (3) was isolated from Halimium viscosum. Their structures were determined to possess a seven-membered ring fused with a five-membered ring, sphenolobane-type diterpene. The absolute configurations of 1 and 2 have not been determined, while tormesol (3) has been proposed to have the S-configuration at the C-13 position by NMR analysis. We have succeeded in total synthesis of 1, 2, and 3 and determined their absolute configurations. As illustrated in our retrosynthetic analysis of 1, 2, and 3, we planned to synthesize the seven-membered ring system including a tri-substituted double bond using ring closing metathesis reaction and the five-membered ring system by aldol reaction, followed by conjugate reduction of the key intermediate 7. The cyclization precursor 12 was synthesized from ethyl acetoacetate (13). The precursor 12 did not produce seven-membered ring compound 11 using Grubbs' reagent or Schrock's reagent. Therefore, 12 was reduced to alcohol, which was protected by TES, MOM, and Ac groups (14, 15, 16). Compound 17 was obtained from compound 14 using Grubbs' reagent in 94% yield (Table 1). The optically active compound 9 was prepared from 10 using (S)-(-)-phenylethylamine as a chiral auxiliary. The optical purity was 97%ee by HPLC (CHIRALCEL OD-H). The key intermediate 7 was derived from keto nitrile 8 by aldol reaction in 97% yield. Compound 25 was obtained by conjugate reduction of 7 using Mg/MeOH. Compounds 1 and 2 were derived from compound 25 (Schemes 4, 5). Tormesol (3) was synthesized from compound 25 by methylation of the cyano group and alkylation of the resulting ketone (Scheme 6). The spectral data including the specific rotation of compounds 1 and 2 were identical with those of the natural products, establishing their absolute configurations. The spectral data of 3 was also identical with those of the natural product. However, the specific rotation was opposite to that of the natural one, supporting the assigned absolute configuration.
- 天然有機化合物討論会の論文
- 2001-09-01
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