Studies on The Synthesis of Sesquiterpenes as Host-specific Phytotoxins Directed towards Novel Insecticides.

作为宿主特异性植物毒素的倍半萜烯的合成研究，针对新型杀虫剂。

• 批准号: 62560116
• 负责人: KITAHARA Takeshi
• 金额: $ 1.28万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-62560116/
• 关键词: Host-specific phytotoxins; phytotoxins; Sporogen-AO 1; Gigantenone; Chiral synthesis Stereoselective synthesis; 植物病原菌毒素; 高選択的合成; 光学活性体合成; ファゼオリノン; フォメノン; 胞子形成因子

Studies on phytotoxins produced by host-specific fungi againdt plants have been paid much attention to clarify the mode of action as well as to develope new insecticides. The amount of these pathogenic toxins, however, not sufficient for biological study, because they are not much available from natural sources. The target of this project is the synthesis of these pathogenic sesquiterpenes to afford natural isomers and their analogs in optically pure forms in substantial amount for biological study.Starting from the hydroxyester with 98.4% e.e. prepared by the asymmetric reduction with bakers yeast, chiral synthesis of sporogen-AO 1( 13-desoxyphomenone ) was achieved in overall 8.4 % yield through 20 steps. By the establishment of this efficient method, general route to afford these pathogenic eremophilane sesquiterpenes was explored. Thus, gigantenone, epi-gigantenone, phomenone ,phase-olinone and analogs were obtained. Using these samples, biological studies is going on, and preliminary experiment showed that even epimer has 60-70% activity of natural isomers. Further studies may reveal biological meaning of these sesquiterpene as pthogens against plants and as sporogenic substances against fungi.

对寄主特异性真菌针对植物产生的植物毒素的研究受到广泛关注，以阐明其作用方式以及开发新的杀虫剂。然而，这些致病毒素的数量不足以进行生物学研究，因为它们不能从天然来源中获得。该项目的目标是合成这些致病性倍半萜，以提供大量光学纯形式的天然异构体及其类似物，用于生物学研究。从具有 98.4% e.e. 的羟基酯开始。通过面包酵母的不对称还原制备孢子原-AO 1（13-脱氧佛酮），经过20步手性合成，总产率8.4%。通过建立这种有效的方法，探索了提供这些致病性eremophilane倍半萜的一般途径。由此，得到了牛烯酮、表牛烯酮、福孟酮、相油酮及其类似物。利用这些样品，正在进行生物学研究，初步实验表明，即使是差向异构体也具有天然异构体60-70%的活性。进一步的研究可能揭示这些倍半萜烯作为对抗植物的病原体和对抗真菌的产孢物质的生物学意义。

项目成果

Fumio Sugawara.;Takeshi Kitahara.;Kenji Mori.: Agric.Biol.Chem.Plant＆Cell Physiol. (1989)

菅原文雄.;北原武.;森健二.:农业.生物.化学.植物与细胞生理学(1989)

Fumio,Sugawara;Takeshi,Kitahara;Kenji,Mori: Agric-Biol,Chem.or Plant ＆ Cell Physiol. (1989)

Fumio，菅原；Takeshi，Kitahara；Kenji，Mori：农业生物、化学或植物与细胞生理学（1989）。

Takeshi,Kitahara;Hiroshi,Kurata;Kenji,Mori: Tefrahedron. 45. (1989)

Takeshi，北原；Hiroshi，Kurata；Kenji，Mori：四面体。

Takeshi Kitahara; Hitoshi Kurata; Kenji Mori,: "Chiral Synthesis of Phytopathogenic Toxins, Gigantenone, Phomenone, Phaseolinone and Their Analogs" Tetrahedron. 45. (1989)

北原武；

Takeshi Kitahara; Hitoshi Kurata; Kenji Mori,: "Efficient Synthesis of the Natural Enautiomers of Sporogen-AO 1 (13-Desoxyphomenone), A Sporogenic Sesquiterpene from Aspergillus oryzae." Tetrahedron. 44. 4339-4349 (1988)

北原武；