Synthetic Study of Naturally Occurring Indoles Possessing Various Substituents on Benzene Moiety.

苯部分具有各种取代基的天然吲哚的合成研究。

• 批准号: 03671017
• 负责人: MURAKAMI Yasuoki
• 金额: $ 1.28万
• 依托单位: TOHO 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: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03671017/
• 关键词: Pyrrole; Indole; Alkaloid; Regiospecific; Acylation; Bromination; Hymenin; 脱ブロム化; カルボリンアルカロイド; ウィティッヒ反応; ベックマン転位; ピロ-ル; インド-ル

A new synthetic methodology of indole nucleus starting with ethyl pyrrole-2-carboxylate (1) and its application were examined as follows.1. The C_4-acylation of 1 by Friedel-Crafts reaction was examined, and the scope and limitation were established (1 -> 2). On the basis of it, a new synthetic route for indoles possessing various substituents on benzene moiety was developed.2. By applying the above method, the synthesis of 9-methoxybenz[f] indole (6) was successful, and naturally occurring eupolauramine (7) was synthesized from 6.3. Regioselectivity was found in the bromination of a methoxyindole derived from 1, and thus the regioselective bromination was systematically carried out on various methoxyindoles.4. A synthesis of naturally occurring hymenin (11) from marine sponge was examined, and we have obtained the intermediate compound 14 at the present time.

本文以吡咯-2-羧酸乙酯（1）为起始原料，研究了吲哚核的合成新方法及其应用.考察了1的C_4-酰基化反应，确定了反应的范围和限度（1 -> 2）。在此基础上，发展了一条新的合成苯上具有多种取代基的吲哚类化合物的路线.应用上述方法，成功地合成了9-甲氧基苯并[f]吲哚（6），并以6.3为原料合成了天然存在的优泊金胺（7）。在1衍生的甲氧基吲哚的溴化反应中发现了区域选择性，从而系统地对各种甲氧基吲哚进行了区域选择性溴化反应.研究了从海绵中天然存在的膜蛋白（11）的合成，目前我们已经得到了中间体化合物14。

项目成果

Y.Murakami: "The Friedel-Crafts Acylation of Ethyl Pyrrole-2-carboxylate.Scope,Limitations,and Application to Synthesis of 7-Substituted Indoles." Heterocycles.27. 1855-1860 (1988)

Y.Murakami：“吡咯-2-甲酸乙酯的弗里德尔-克拉夫茨酰化。范围、局限性以及在 7-取代吲哚合成中的应用。”

M.Tani: "beta-Acylation of Pyrrole Ring by the Friedel-Crafts Acylation of Ethyl Pyrrole-2-carboxylate, Scope, and Limitation [Synthetic Studies on Indoles and Related Compounds. XXXIV]." In preparation (will be submitted to Chem.Pharm.Bull.).

M.Tani：“吡咯环的β-酰化通过吡咯-2-甲酸乙酯的弗里德尔-克来福特酰化、范围和限制[吲哚和相关化合物的合成研究。XXXIV]”。