著者

柳屋 光俊 続木 一夫 渡辺 隆啓 中島 康之 松田 冬彦 長谷川 和夫 松本 毅

出版者

天然有機化合物討論会

雑誌

天然有機化合物討論会講演要旨集

巻号頁・発行日

no.22, pp.635-641, 1979-09-20

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Pederin, a potent insect poison isolated from paedrus fuscipes, exhibits various interesting physiological activities, such as inhibition of mitosis in HeLa cell and blocking of protein synthesis at concentrations of 1-10 ng/me. We describe here the first total synthesis of pederin. Asymmetric Synthesis of Pedaldehyde Derivatives. Asymmetric reduction of ketone 14 was examined under various conditions. The desired alcohol 13R was obtained by reduction with LiAlH_4 in ether-toluene (54: 46) at -123°in 74% e.e. The alcohol 13R was converted stereoselectively to pedamide 28 (Fig. 4,5). Synthesis of N-acyl aminoacetals. A new general method for the synthesis of N-acyl aminoacetals was developed and the method was applied to the synthesis of pederin, starting from (+)-pederic acid and (+)-pedamide.

著者

田中 正泰 針ヶ谷 弘子 鎌田 樹志 氏原 一哉 橋本 勝 橋本 貴美子 松田 冬彦 柳屋 光俊 白濱 晴久 奥野 智旦

出版者

天然有機化合物討論会実行委員会

雑誌

天然有機化合物討論会講演要旨集 34 (ISSN:24331856)

巻号頁・発行日

pp.110-117, 1992-09-10 (Released:2017-08-18)

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Ohwaraitake is Japanese name of a poisonous mushroom Gymnopilus spectabilis and means "a loud laugh mushroom". Accidental ingestion of it causes hallucinosis and abnormal behavior. A hallucinogenic mushroom contains usually psilocybin or its analogues but it is reported that any psilocybin or its congenor does not found in Japanese Ohwaraitake. The toxic symptoms suggest that any neuroexcitatory substance must be contained. The isolation was carried out monitoring depolarizing activity on the new born rat spinal cord. 1. Chromatographical fractionation and bisassay showed that the neuroexcitatory active compounds were gimnopilins (G) which were known as bitter principles of this fungus. Further fractionation revealed that G (1) was inactive and activities of G (2) increased from n=7 to n=5 and besides, G (2), which was newly isolated this time, was more active than G (2). 2. The structure of the new G was determined by the chemical degradation as formula 3. 3. The Chirality of hydroxymethylglutamic acid (HMGA) part was determined as S configuration by the acquisition of (R)-mevalonaloctone through LiBH4 reduction or G (1 and 2). 4. G (2) does not work as an ion carrier probably, since it does not particularly take metal ion from aqueous solution into an organic solvent. 5. Determination of the chirality of tert-alcohols in gymnoprenol (G'), that is, G without HMGA part, was attempted. Eight isomers of the model compounds corresponding to G' (m=2, n=4) were synthesized and were not discriminated by HPLC and NMR. Since two diastereoisomers of MTP-ethoxy-methoxy derivatives of G' (m=1, n=2) were distinguished by ^1H and ^<19>FNMR, these derivatives may be applicable to identification of the synthetic and the natural G'.

著者

田中 正泰 針ヶ谷 弘子 鎌田 樹志 氏原 一哉 橋本 勝 橋本 貴美子 松田 冬彦 柳屋 光俊 白濱 晴久 奥野 智旦

出版者

天然有機化合物討論会

雑誌

天然有機化合物討論会講演要旨集

巻号頁・発行日

no.34, pp.110-117, 1992-09-10

---

Ohwaraitake is Japanese name of a poisonous mushroom Gymnopilus spectabilis and means "a loud laugh mushroom". Accidental ingestion of it causes hallucinosis and abnormal behavior. A hallucinogenic mushroom contains usually psilocybin or its analogues but it is reported that any psilocybin or its congenor does not found in Japanese Ohwaraitake. The toxic symptoms suggest that any neuroexcitatory substance must be contained. The isolation was carried out monitoring depolarizing activity on the new born rat spinal cord. 1. Chromatographical fractionation and bisassay showed that the neuroexcitatory active compounds were gimnopilins (G) which were known as bitter principles of this fungus. Further fractionation revealed that G (1) was inactive and activities of G (2) increased from n=7 to n=5 and besides, G (2), which was newly isolated this time, was more active than G (2). 2. The structure of the new G was determined by the chemical degradation as formula 3. 3. The Chirality of hydroxymethylglutamic acid (HMGA) part was determined as S configuration by the acquisition of (R)-mevalonaloctone through LiBH4 reduction or G (1 and 2). 4. G (2) does not work as an ion carrier probably, since it does not particularly take metal ion from aqueous solution into an organic solvent. 5. Determination of the chirality of tert-alcohols in gymnoprenol (G'), that is, G without HMGA part, was attempted. Eight isomers of the model compounds corresponding to G' (m=2, n=4) were synthesized and were not discriminated by HPLC and NMR. Since two diastereoisomers of MTP-ethoxy-methoxy derivatives of G' (m=1, n=2) were distinguished by ^1H and ^<19>FNMR, these derivatives may be applicable to identification of the synthetic and the natural G'.