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.

一些植物病原真菌孢子中含有干扰孢子萌发的自抑制物质。1982年，Mayor和他的同事报道了从真菌炭疽菌gloeosporioide中分离出一种自我抑制剂gloeosporone。以该化合物的合成为目的，考察其构效关系。在资助的第一年，我们完成了gloeosporone的外消旋修饰及其非对映异构体的合成。在此基础上，我们重点研究了这些旋光性化合物的合成。应用刘易斯酸催化(S)-1-（1-萘基）异氰酸乙酯（皮尔克尔试剂）制备(dl)-1-三烯-8-醇基氨基甲酸酯，得到了非对映异构体氨基甲酸酯的混合物。各同分异构体以纯形式分离后，用氢化铝锂还原再生具有光学活性的1-癸烯-8-醇。通过追踪外消旋格罗孢酮的合成过程，完成了(+)-和(-)-格罗孢酮及其立体异构体的合成。但经生物学试验，这些化合物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接受调查。

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.36. 3928-3932 (1988)

Hiroshi IRIE.：Chem.Pharm.Bull.36。

Hiroshi,IRIE.: Chem.Pharm.Bull.36. 3134-3137 (1988)

Hiroshi，IRIE.：Chem.Pharm.Bull.36。

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

Hiroshi IRIE.：Chem.Pharm.Bull.35。

Tamio Ueno: "Studies in Natural Products Chemistry Vol.?Edited by Atta-ur-Rahman" Elsevier(Amsterdam-Oxford-New York-Tokyo), (1990)

Tamio Ueno：“天然产物化学研究卷？由 Atta-ur-Rahman 编辑”Elsevier（阿姆斯特丹-牛津-纽约-东京），（1990 年）