取代8-羟基喹啉钌络合物催化Friedländer反应合成喹啉衍生物
收稿日期: 2022-10-28
修回日期: 2022-12-02
网络出版日期: 2023-02-15
基金资助
国家自然科学基金(22072099); 教育部春晖计划基金(192635)
Synthesis of Quinoline Derivatives by Friedländer Reaction Catalyzed by Ruthenium Complexes of Substituted 8-Hydroxyquinoline
Received date: 2022-10-28
Revised date: 2022-12-02
Online published: 2023-02-15
Supported by
National Natural Science Foundation of China(22072099); Chunhui Program of Ministry of Education(192635)
Friedländer喹啉合成法是以邻胺基芳基醛或酮与有α-亚甲基的酮环化制备喹啉的反应, 报道了一种喹啉钌络合物催化Friedländer法合成喹啉的方法. 首先, 以8-羟基喹啉钌络合物为催化剂, 对模板反应邻氨基苯甲醇和苯乙酮合成2-苯基喹啉进行了反应条件优化实验. 重点对比研究了8-羟基喹啉钌络合物配体上不同取代基对反应收率的影响, 其中5-甲基-8-羟基喹啉(1e)钌络合物催化邻氨基苯甲醇和苯乙酮合成2-苯基喹啉获得了73%的最高收率. 结合IR, UV以及密度泛函理论(DFT)计算讨论了配体结构与催化性能之间的关系. 提出了β-H消除形成醛过渡态, 交叉aldol反应再亚胺环化, 最后脱水生成目标产物的可行机理. 以(1e)3Ru为催化剂, 在优化的反应条件下进行了底物扩展研究, 以69%~94%的收率合成了32个不同取代的喹啉衍生物, 验证了方法的普适性.
关键词： 8-羟基喹啉钌络合物; 催化; Friedländer反应
朱玥 , 陈璐 , 赵静 , 孙庆荣 , 杨维清 , 付海燕 , 马梦林 . 取代8-羟基喹啉钌络合物催化Friedländer反应合成喹啉衍生物[J]. 有机化学, 2023 , 43(7) : 2528 -2542 . DOI: 10.6023/cjoc202210036
The Friedländer quinoline synthesis method is a reaction of o-aminoaryl aldehyde or ketone with methyl ketone to obtain quinoline. In this paper, a method for synthesizing quinoline catalyzed by ruthenium complexes of quinoline was reported. Using 8-hydroxyquinoline ruthenium complex as catalyst, the reaction conditions were optimized. The effects of different substituents of 8-hydroxyquinoline ruthenium complexes on the reaction yield were comparatively studied. Among them, 5-methyl-8-hydroxyquinoline (1e) ruthenium complex catalyzed the synthesis of 2-phenylquinoline from o-aminobenzyl alcohol and acetophenone with the highest yield of 73%. The relationship between ligand structure and catalytic performance was discussed by combining IR, UV and density functional theory (DFT) calculations. A possible mechanism was proposed, which included the formation of aldehyde transition state through β-H elimination, cross aldol reaction, imination cyclization and finally dehydration to produce the target product. Using (1e)3Ru as catalyst, 32 quinoline derivatives with different substitutions were synthesized with 69%~94% yields under the optimized reaction conditions, which confirmed the generality of this method.
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