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

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。

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.