Development of hydrogen transfer reactions catalyzed by iridium complexes and their applications to the synthesis of nitrogen heterocycles

铱配合物催化氢转移反应的进展及其在氮杂环合成中的应用

基本信息

批准号：
14550806
负责人：
YAMAGUCHI Ryohei
金额：
$ 1.73万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2003
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14550806/
关键词：
iridium catalyst alcohol amine N-alkylation nitrogen heterocycle hydrogen transfer reaction

项目摘要

In recent years, much attention has been focused on the chemistry of iridium complexes bearing a pentamethylcyclopentadienyl (Cp^*) ligand. During the course of our investigation on the chemistry of Cp^* iridium complexes, we found a catalytic activity of [Cp^*IrCl_2]_2 toward hydrogen transfer reactions between organic molecules. In this research project, we have studied on the hydrogen transfer reactions catalyzed by Cp^* iridium complexes and their applications to the synthesis of nitrogen heterocycles.First, we have found a new catalytic oxidative cyclization of amino alcohols. Indole derivatives were synthesized in good to excellent yields from 2-aminophenethyl alcohols by means of a [Cp^*IrCl_2]_2 / K_2CO_3 catalytic system. This catalytic system was also effective for syntheses of 1,2,3,4-tetrahydroquinolines from 3-(2-aminophenyl)propanols and 2,3,4,5-tetrahydro-1-benzazepine from 4-(2-aminophenyl)butanol.Next, we have found an efficient catalytic system for N-alkylation of primary amines with alcohols. As an example, the reaction of aniline with benzyl alcohol in the presence of catalytic amounts of [Cp^*IrCl_2]_2 and K_2CO_3 gave N-benzylaniline in excellent yield. This catalytic system was applicable to a wide variety of amines and alcohols.On the basis of above results, we have found a new catalytic system for N-heterocyclization of primary amines with diols. Pyrrolidine, piperidine, azepane and morpholine derivatives could be synthesized in good yields by the reaction of benzylamine with 1,4-, 1,5-and 1,6-diols in the presence of Cp^*Ir catalyst and base.We also examined the transfer hydrogenation of quinolines using 2-propanol as a hydrogen source. 1,2,3,4-Tetrahydroquinoline derivatives were synthesized in good yields by regio-and chemoselective transfer hydrogenation catalyzed by Cp^*Ir catalyst.

近年来，带有五甲基环戊二烯基（Cp^*）配体的铱配合物的化学受到了广泛关注。在我们对 Cp^* 铱配合物化学的研究过程中，我们发现 [Cp^*IrCl_2]_2 对有机分子之间的氢转移反应具有催化活性。在本研究项目中，我们研究了Cp^*铱配合物催化的氢转移反应及其在氮杂环合成中的应用。首先，我们发现了一种新的氨基醇催化氧化环化反应。利用[Cp^*IrCl_2]_2 / K_2CO_3催化体系以2-氨基苯乙醇为原料合成了吲哚衍生物，收率良好。该催化体系对于从 3-(2-氨基苯基)丙醇合成 1,2,3,4-四氢喹啉和从 4-(2-氨基苯基)丁醇合成 2,3,4,5-四氢-1-苯并氮杂卓也有效。接下来，我们发现了一种有效的催化系统，用于伯胺与醇的 N-烷基化。例如，苯胺与苯甲醇在催化量的[Cp^*IrCl_2]_2和K_2CO_3存在下反应，以优异的收率得到N-苯甲基苯胺。该催化体系适用于多种胺和醇。基于上述结果，我们找到了一种新的伯胺与二醇N-杂环化催化体系。在 Cp^*Ir 催化剂和碱存在下，苄胺与 1,4-、1,5-和 1,6-二醇反应，可以高产率合成吡咯烷、哌啶、氮杂环庚烷和吗啉衍生物。使用2-丙醇作为氢源进行喹啉的转移氢化。通过 Cp^*Ir 催化剂催化的区域选择性和化学选择性转移氢化，以良好的收率合成了 1,2,3,4-四氢喹啉衍生物。