水杨酮烯胺化合物的无催化剂合成  

Catalyst-free Synthesis of Salicyl Enaminone Compounds

作　　者：刘仁明 黄雄 刘雄利[1] 张敏[1] 彭礼军[1] LIU Ren-ming;HUANG Xiong;LIU Xiong-li;ZHANG Min;PENG Li-jun(National & Local Joint Engineering Research Center for the Exploition of Homology Resources of Medicine and Food, Guizhou University, Guiyang 550025, China;Yongkang No. 2 Middle School, Jinhua 321300, China)

机构地区：[1]贵州大学西南药食两用资源开发利用技术国家地方联合工程研究中心,贵州贵阳550025 [2]永康市第二中学,浙江金华321300

出　　处：《合成化学》2021年第12期1071-1076,共6页Chinese Journal of Synthetic Chemistry

基　　金：贵州大学培育项目(202078)。

摘　　要：基于新的合成方法学研究,以色酮-3-甲酸1与二级胺2为原料,在无催化剂条件下,在二氯甲烷中发生Michael加成/脱羧/开环反应,合成了15个水杨酮烯胺化合物3a~3o,产率72%~92%,其结构经^(1)H NMR,^(13)C NMR和HR-MS(ESI-TOF)表征,并进一步通过单晶确定化合物3o的结构。该方法不需要任何催化剂,利用色酮-3-甲酸的高活性和二级胺的亲核性发生Michael加成反应,生成的中间体不稳定,发生脱羧和开环反应产生目标产物水杨酮烯胺化合物3,可以为天然产物的全合成提供多样性的合成子或直接作为催化剂配体。Based on the study of new synthesis methodology,fiveten salicyl enaminone compounds 3a~3o were synthesized by Michael addition/decarboxylation and ring opening reaction of chromone-3-formic acid 1 and secondary amine 2 in dichloromethane at room temperature without catalyst.The yields were 72%~92%.The structures were characterized by ^(1)H NMR,^(13)C NMR and HR-MS(ESI-TOF).The configuration of compound 3o was further determined by the single crystal.The method does not need any catalyst,uses the high activity of chromone-3-formic acid and the nucleophilic property of secondary amine to produce Michael addition reaction,the generated intermediate is unstable,decarboxylation and ring opening reaction to produce the desired salicyl enaminone compounds 3,which can provide a variety of synthons for the complete synthesis of natural products or serve as catalyst ligands.

关 键 词：色酮-3-甲酸 二级胺 MICHAEL反应 加成反应 水杨酮烯胺 合成 

分 类 号：O626.13[理学—有机化学] O623.7[理学—化学]