铜盐催化5-乙炔基-噁唑烷-2,4-二酮与芳香伯胺的脱羧炔丙氨化反应  

Copper Salt-catalyzed Decarboxylative Amination of 5-Ethynyl-oxazolidine-2,4-dione and Aromatic Primary Amines

作　　者：孙婷珈 孙国银 周鸣强[1,2] 赵建强 葛真真[1,2] 袁伟成 SUN Tingjia;SUN Guoyin;ZHOU Mingqiang;ZHAO Jianqiang;GE Zhenzhen;YUAN Weicheng(National Engineering Research Center of Chiral Drugs,Chengdu Institute of Organic Chemistry,Chinese Academy of Sciences,Chengdu 610041,China;University of Chinese Academy of Sciences,Beijing 100049,China;Institute for Advanced Study,Chengdu University,Chengdu 610106,China)

机构地区：[1]中国科学院成都有机化学研究所手性药物国家工程研究中心,四川成都610041 [2]中国科学院大学,北京100049 [3]成都大学高等研究院,四川成都610106

出　　处：《合成化学》2024年第12期1013-1020,共8页Chinese Journal of Synthetic Chemistry

基　　金：国家自然科学基金资助项目(22302021,22271027,22171029)。

摘　　要：α-四取代氨基酸衍生物作为一种重要的非天然氨基酸单元,广泛存在于药物分子、天然产物以及生物活性分子中。铜催化乙炔基取代的环状碳酸酯类或氨基甲酸酯类化合物的脱羧反应是有机化学领域的研究热点,设计并合成了底物5-乙炔基-噁唑烷-2,4-二酮(EODO),并将其用于铜盐催化乙炔基取代的噁唑烷酮与芳香伯胺的脱羧炔丙氨化反应。该反应以良好到优秀的收率(58%~94%)合成了12个结构新颖的α-四取代氨基酸衍生物(3a~3l),其结构经^(1)H NMR、^(13)C NMR和HR-MS(ESI-TOF)表征。Alpha-tetrasubstituted amino acid derivatives,as a class of important non-natural amino acid moieties,are widely found in drug molecules,natural products and biologically active molecules.The copper-catalyzed decarboxylation of ethynyl-substituted cyclic carbonate or carbamate is a hot topic in organic chemistry.In this article,we have designed and synthesized the substrate of 5-ethynyloxazolidine-2,4-diones(EODO).The copper-catalyzed decarboxylative propargylic amination reaction between EODO and aromatic primary amines enables the synthesis of twelve novelα-tetrasubstituted amino acid derivatives(3a~3l)with good to excellent yields(58%~94%).The products were characterized by ^(1)H NMR,^(13)C NMR and HR-MS(ESI-TOF).

关 键 词：α-四取代氨基酸衍生物 5-乙炔基-噁唑烷-2 4-二酮(EODO) 脱羧反应 炔丙位氨化 芳香伯胺 

分 类 号：O621.3[理学—有机化学]