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，已经关注了虹膜络合物的化学，并带有五甲基环戊二烯基（CP^*）配体。在研究CP^*虹膜络合物化学的过程中，我们发现[Cp^* IRCL_2] _2的催化活性朝着有机分子之间的氢转移反应。在该研究项目中，我们研究了由Cp^* iridium Compliepes催化的氢转移反应及其在合成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氧化环化。通过[CP^*IRCL_2] _2 / K_2CO_3催化系统从2-氨基苯基醇中良好至优异的产率合成吲哚衍生物。该催化系统对于来自3-（2-氨基苯基）丙醇的1,2,3,4-四氢喹啉的合成也有效例如，在存在催化量的[CP^*IRCL_2] _2和K_2CO_3的情况下，苯胺与苄醇的反应给出了n-苯甲酰氨酸的良好产率。该催化系统适用于各种胺和酒精。在上述结果的基础上，我们发现了一种新的催化系统，用于二醇二胺的N-杂环化。吡咯烷，哌啶，偶氮和吗啡衍生物可以通过苄胺与1,4-，1,5和1,6-二醇的反应以良好的产量合成，而在CP^*IR催化剂和碱的存在下，我们还检查了使用2-丙醇源作为Quinoline的转移氢的转移。 1,2,3,4-四氢喹啉衍生物通过cp^*ir催化剂催化的区域和化学选择性转移氢化以良好的收率合成。