脯氨酰胺衍生的新型噻吩-叔胺手性N-氧化物的合成  

Synthesis of Prolinamide-derived Novel Thiophene-tertiary-amine-based Chiral N-oxides

作　　者：田方丽 王宇恒 张磊[1] 刘雄利[1] 邓国栋[1] TIAN Fangli;WANG Yuheng;ZHANG Lei;LIU Xiongli;DENG Guodong(National&Local Joint Engineering Research Center for the Exploition of Homology Resources of Medicine and Food,Guizhou University,Guiyang 550025,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

出　　处：《合成化学》2023年第9期702-706,共5页Chinese Journal of Synthetic Chemistry

基　　金：贵州省基础研究项目(黔科合基础-ZK[2022]一般144号)。

摘　　要：叔胺手性N-氧化物配体的结构多样性合成对金属不对称催化反应具有重要意义。为了拓展手性N-氧化物配体的化学空间,以光学纯的脯氨酰胺或羟脯氨酰胺(1)与各种取代的噻吩-2-甲醛(2)发生缩合环化反应,生成缩合的中间体(3),然后中间体(3)中的氮原子在氧化剂m-CPBA(间氯过氧苯甲酸)的作用下发生N-氧化反应,室温下合成了10个新型噻吩-叔胺手性N-氧化物(4a~4j),总产率41%~57%,dr值为18/1~>20/1,其结构经1H NMR,13C NMR和HR-MS(ESI-TOF)表征。该类手性N-氧化物以L-脯氨酰胺或羟脯氨酰胺作为手性源制备,今后可以为金属不对称催化提供新配体筛选。The structural diversity synthesis of tertiary amine-derived chiral N-oxide ligands is of great significance for metal asymmetric catalytic reactions.In this paper,using optically pure prolamides or hydroxyprolamides(1)as the chiral source,the intermediates(3)were synthesized by condensation cyclization with various substituted thiophene-2-formaldehydes(2),and then the nitrogen atom in the intermediates(3)was oxidized under the action of chloro perbenzoic acid,an oxidant,to provide 10 prolinamide-derived thiophene-tertiary-amine-based chiral N-oxides(4a~4j)in 41%~57%overall yield and dr 18/1~>20/1.The structures of products(4)were characterized by 1H NMR,13C NMR and HR-MS(ESI-TOF).These chiral N-oxide compounds,based on L-prolinamides serving as chiral sources,can provide new ligand screening for Lewis acid asymmetric catalysis in the future.

关 键 词：脯氨酰胺 噻吩-2-甲醛 叔胺手性N-氧化物 新配体 缩合环化反应 N-氧化反应 

分 类 号：O626.13[理学—有机化学] O623.7[理学—化学]