Synthetic Studies of Gloeosporone, A Self-Inhibitor for Germination of Spores of Colletotrichum gloeosporioides

胶孢炭疽菌孢子萌发自抑制剂Gloeosporone的合成研究

• 批准号: 63570997
• 负责人: IRIE Hiroshi
• 金额: $ 1.34万
• 依托单位: Nagasaki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-63570997/
• 关键词: Spores of Fungus; Self-inhibito; Gloeosporone; Carbamate formation; Resolution; 天然物全合成; 植物病原菌; さび菌胞子; 立体異性体; 光学活性体の合成; 炭そ病菌; 胞子自己発芽抑制因子

Some spores of plant pathogenic fungi possess the compounds, named as self-inhibitor, which interfere the germination of spores. In 1982, Mayor and his coworkers reported the isolation of a self-inhibitor, gloeosporone, from the fungus Colletotrichum gloeosporioide. We aimed at the synthesis of the compound to investigate the structure-activity relationship.In the first year of the grant, we accomplished the synthesis of gloeosporone as a racemic modification along with its diastereoisomer. Based on the result, we focused on the synthesis of these compounds in optically active forms. Application of Lewis acid catalysed preparation of the carbamates on (dl)-1-tridecene-8-ol with (S)-1-(1-naphthyl)ethyl isocyanate (Pirkle's reagent) gave a mixture of the diastereoisomeric carbamates. After separation of each isomer in pure form, the optically active 1-decene-8-ols were regenerated by reduction with lithium aluminum hydride. By tracing the procedure for synthesis of racemic gloeosporone, the synthesis of (+)- and (-)-gloeosporone and their stereoisomers were completed. The biological test of these compounds synthesized, however, have the weak activity as a self-inhibitor. The effort to disclose the discrepancy between the reported data and our results is under investigation.

一些植物病原真菌的孢子具有干扰孢子萌发​​的化合物，称为自抑制剂。 1982 年，Mayor 和他的同事报道了从真菌胶孢炭疽菌 (Colletotrichum gloeosporioide) 中分离出一种自我抑制剂——胶孢菌素 (gloeosporone)。我们以该化合物的合成为目标，研究其构效关系。在资助的第一年，我们完成了外消旋修饰的胶孢酮及其非对映异构体的合成。基于该结果，我们专注于这些光学活性形式化合物的合成。应用路易斯酸催化在(dl)-1-十三碳烯-8-醇上与(S)-1-(1-萘基)乙基异氰酸酯(Pirkle试剂)制备氨基甲酸酯，得到非对映异构氨基甲酸酯的混合物。在以纯形式分离每种异构体后，通过用氢化铝锂还原来再生光学活性的1-癸烯-8-醇。通过追踪外消旋炭疽菌素的合成过程，完成了(+)-和(-)-炭疽菌素及其立体异构体的合成。然而，这些合成的化合物的生物学测试表明其作为自抑制剂的活性较弱。披露报告数据与我们的结果之间差异的努力正在调查中。

项目成果

Hiroshi Irie, Masatska Nishimura, and Morihiro Yoshida: "Lewis Acid Catalysed Preparation of some Carbamates and Sulphonylureas. Application to the Determination of Enantiomeric Purity of Chiral Alcohols" J. Chem. Soc.Perkin Trans. I. 1209-1210 (1989)

Hiroshi Irie、Masatska Nishimura 和 Morihiro Yoshida：“路易斯酸催化制备一些氨基甲酸酯和磺酰脲。应用于测定手性醇的对映体纯度”J. Chem。

Hiroshi IRIE.: Chem.Pharm.Bull.35. 2598-2601 (1987)

Hiroshi IRIE.：Chem.Pharm.Bull.35。

Hiroshi IRIE.: Chem.Pharm.Bull.36. 3928-3932 (1988)

Hiroshi IRIE.：Chem.Pharm.Bull.36。

Tamio Ueno, Tetsu Tsurushima, Hiroshi Fukamin and Hiroshi Irie: Studies in Natural Products Chemistry Vol X Chemistry of Self-Inhibitors of Fungal Germination (Edited by Atta-ur-Rahman). Elsevier, Amsterdam-Oxford-New York- Tokyo, (1990)

Tamio Ueno、Tetsu Tsurushima、Hiroshi Fukamin 和 Hiroshi Irie：天然产物化学研究卷 X 真菌萌发自我抑制剂的化学（由 Atta-ur-Rahman 编辑）。

Hiroshi Irie: "Lewis Acid Catalysed Preparation of some Carbamates and Sulphonylureas.Application to the Determination of Enantiomeric Purity of Chiral Alcohols" J.Chem.Soc.,Perkin Transaction I. 1989. 1209-1210 (1989)

Hiroshi Irie：“路易斯酸催化制备一些氨基甲酸酯和磺酰脲。应用于测定手性醇的对映体纯度”J.Chem.Soc.，Perkin Transaction I. 1989. 1209-1210 (1989)