- 著者
- 中川 昌子 木内 みどり 小尾 道子 殿塚 雅克 小林 和美 日野 亨 舟越 和久
- 出版者
- 公益社団法人 日本薬学会
- 雑誌
- Chemical and Pharmaceutical Bulletin (ISSN:00092363)
- 巻号頁・発行日
- vol.23, no.2, pp.304-312, 1975
- 被引用文献数
- 17
The reaction of tryptamine with δ-valerolactone in tetralin gave δ-hydroxyamide (3) as the main product and the lactam (4) as the minor product. However, the reaction of 5, 6-dihydro-2-pyrone with tryptamine or aniline afforded a mixture of the corresponding αβ- and βγ-unsaturated lactams, whereas, 2-pyrone did not react with either tryptamine or aniline to give the corresponding pyridone. Cyclization of 3 or 4 by Bischler-Napieralski reaction and followed NaBH<SUB>4</SUB> reduction provided a convement synthesis of 1, 2, 3, 4, 6, 7, 12, 12b-octahydroindolo [2, 3-α] quinolizine (23).
- 著者
- 末宗 洋 林 教行 舟越 和久 秋田 弘幸 大石 武 酒井 浄
- 出版者
- The Pharmaceutical Society of Japan
- 雑誌
- Chemical and Pharmaceutical Bulletin (ISSN:00092363)
- 巻号頁・発行日
- vol.33, no.5, pp.2168-2170, 1985-05-25 (Released:2008-03-31)
- 参考文献数
- 12
- 被引用文献数
- 24 29
(S)-13-Hydroxy-9Z, 11E-octadecadienoic acid, a defensive substance in rice, was synthesized with high enantioselectivity by the reduction of the corresponding ketone with yeasts.
- 著者
- 舟越 和久 稲田 治明 浜名 政和
- 出版者
- The Pharmaceutical Society of Japan
- 雑誌
- Chemical and Pharmaceutical Bulletin (ISSN:00092363)
- 巻号頁・発行日
- vol.32, no.12, pp.4731-4739, 1984-12-25 (Released:2008-03-31)
- 参考文献数
- 14
- 被引用文献数
- 3 5
Isoquinoline 2-oxide (1) reacts with cyanoacetic acid in the presence of Ac2O to afford various types of 1-substituted isoquinolines (2, 4, 6, and 7) and N-ylides (3 and 5a) depending upon the reaction conditions and processing procedures (Table I). The reaction in Ac2O gives initially α-acetoxycarbonyl-1-isoquinolineacetonitrile (2) and 2-isoquinolinio-acetoxycarbonylcyanomethylide (3), and that in Ac2O-dimethylformamide yields only 3. Products 2 and 3 are readily convertible into α-acetyl-1-isoquinolineacetonitrile (4) and 2-isoquinolinio-acetylcyanomethylide (5a), respectively, by processing involving heating. The reaction in ethanol gives ethyl α-cyano-1-isoquinolineacetate (6) and di (1-isoquinolyl) acetonitrile (7). The reaction of 1 with benzoylacetonitrile affords both the corresponding 1-substituted isoquinoline (10) and N-ylide (11). Reactions with ethyl benzoylacetate and, methyl and ethyl acetoacetates produce 1-substituted isoquinolines (12 and 14a, b) and 4-acetoxyisoquinoline (13), no ylide being formed.
- 著者
- 酒井 浄 石黒 靖尚 舟越 和久 上野 貢嗣 末宗 洋
- 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 26 (ISSN:24331856)
- 巻号頁・発行日
- pp.299-306, 1983-09-15 (Released:2017-08-18)
Variously functionalized cyclopentanones are important as starting materials for the synthesis of natural products. We have succeeded in a simple, highly stereospecific synthesis of five membered ring ketone using Wilkinson complex. Thus, the precursors, 1-al-4-enes(4a-e,11,13) prepared in optically active form from D-limonene, (+)-limonen-10-ol and 1-carvone in three steps were submitted for RhCl(PPh_3)_3-catalyzed cyclization in CH_2Cl_2 to afford the cis-3,4-disubstituted cyclopentanones(14-22) in good yield (Table 2). The following results were obtained in this cyclization. 1) In all cases, the cis-3,4-disubstituted cyclopentanones were stereospecifically obtained as the sole products. 2) The cyclization reaction of the six membered lactols(12,13) was found to proceed very slowly even if at high temperature. 3) The cis-3,4-disubstituted cyclopentanones obtained in this method were also found to be applicable for the synthesis of bicyclic ketone(23). 4) The configurations of 3,4-disubstituents in each compounds were clarified by the way of chemical correlation and spectral analyses. Further application for the synthesis of ent-cis,cis-dihydro-nepetalactone(39) will be discussed.
1 0 0 0 OA 15 リモネンを利用した光学活性シクロペンタノイドの合成
- 著者
- 末宗 洋 上野 貢嗣 川原 哲也 小田 晃造 舟越 和久 酒井 浄
- 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 27 (ISSN:24331856)
- 巻号頁・発行日
- pp.108-114, 1985-09-07 (Released:2017-08-18)
In the synthesis of natural products consisting of the basic structure of cyclopentane ring, variously functionalized cyclopentanones are required as starting materials. Previously, we succeeded in a simple, highly stereospecific synthesis of the cis-3,4-disubstituted cyclopentanones by the mild reaction with RhCl(PPh_3)_3. By the application of this newer cyclization reaction, we have succeeded in the synthesis of cis,cis-dihydronepetalactone, prostanoic acid, 8-isoprostanoic acid, (+)-brefeldin A and carbacyclin in the optically active form from limonene or Corey lactone. These compounds were synthesized via the following key steps. 1) 3-(3-Oxobutyl)cyclopentanone was easily converted to the deconjugated bicyclic enone (3→4). 2) The regioselective alkylation of limonene was performed by using s-BuLi-TMEDA (1→8). 3) The cis-3,4-disubstituted cyclopentanone from limonen-10-ol could be converted to the trans-3,4-disubstituted cyclo-pentanone by the epimerization (15→16, 22→23).
- 著者
- 浜名 政和 舟越 和久 執行 洋陸 口野 嘉幸
- 出版者
- The Pharmaceutical Society of Japan
- 雑誌
- Chemical and Pharmaceutical Bulletin (ISSN:00092363)
- 巻号頁・発行日
- vol.23, no.2, pp.346-350, 1975-02-25 (Released:2008-03-31)
- 被引用文献数
- 4 13
The 1, 3-dipolar cycloaddition between quinoline N-oxide (I) and methyl propiolate progressed in the presence of acetic anhydride or hydroquinone to afford methyl α-formyl-2-quinolineacetate (IIa). The reaction with ethyl propiolate in the presence of hydroquinone gave the corresponding ethyl ester (IIb). The reaction of I with methacrylonitrile in the presence of hydroquinone produced cyanohydrin of 2-acetonylquinoline (VIII) or 2-acetonylquinoline (IX) and 2-cyanoquinoline (X). Isoquinoline N-oxide (XI) was less reactive and resisted the reaction with propiolates, but reacted with methacrylonitrile in the presence of hydroquinone to give 1-acetonyl-isoquinoline (XII), 1-cyanoisoquinoline (XIII) and isoquinoline.
1 0 0 0 15 リモネンを利用した光学活性シクロペンタノイドの合成
- 著者
- 末宗 洋 上野 貢嗣 川原 哲也 小田 晃造 舟越 和久 酒井 浄
- 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
- 巻号頁・発行日
- vol.27, pp.108-114, 1985
In the synthesis of natural products consisting of the basic structure of cyclopentane ring, variously functionalized cyclopentanones are required as starting materials. Previously, we succeeded in a simple, highly stereospecific synthesis of the cis-3,4-disubstituted cyclopentanones by the mild reaction with RhCl(PPh_3)_3. By the application of this newer cyclization reaction, we have succeeded in the synthesis of cis,cis-dihydronepetalactone, prostanoic acid, 8-isoprostanoic acid, (+)-brefeldin A and carbacyclin in the optically active form from limonene or Corey lactone. These compounds were synthesized via the following key steps. 1) 3-(3-Oxobutyl)cyclopentanone was easily converted to the deconjugated bicyclic enone (3→4). 2) The regioselective alkylation of limonene was performed by using s-BuLi-TMEDA (1→8). 3) The cis-3,4-disubstituted cyclopentanone from limonen-10-ol could be converted to the trans-3,4-disubstituted cyclo-pentanone by the epimerization (15→16, 22→23).
- 著者
- 中川 昌子 木内 みどり 小尾 道子 殿塚 雅克 小林 和美 日野 亨 舟越 和久
- 出版者
- 公益社団法人日本薬学会
- 雑誌
- CHEMICAL & PHARMACEUTICAL BULLETIN (ISSN:00092363)
- 巻号頁・発行日
- vol.23, no.2, pp.304-312, 1975
- 被引用文献数
- 17
The reaction of tryptamine with δ-valerolactone in tetralin gave δ-hydroxyamide (3) as the main product and the lactam (4) as the minor product. However, the reaction of 5, 6-dihydro-2-pyrone with tryptamine or aniline afforded a mixture of the corresponding αβ- and βγ-unsaturated lactams, whereas, 2-pyrone did not react with either tryptamine or aniline to give the corresponding pyridone. Cyclization of 3 or 4 by Bischler-Napieralski reaction and followed NaBH<SUB>4</SUB> reduction provided a convement synthesis of 1, 2, 3, 4, 6, 7, 12, 12b-octahydroindolo [2, 3-α] quinolizine (23).