新型手性联吡啶叔胺及其衍生的N-氧化物的合成  

Synthesis of Novel Chiral Bipyridine-tertiary Amine and Their Derived N-Oxides

作　　者：王希瑞 徐客兰 胡盼 姜维艳 刘雄利[1] 邓国栋[1] WANG Xirui;XU Kelan;HU Pan;JIANG Weiyan;LIU Xiongli;DENG Guodong(National&Local Joint Engineering Research Center for The Exploition of Homology Resources of Southwest Medicine and Food,Guizhou University,Guiyang 550025,China;Guizhou Equipmet Manufacturing Vocational College,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 [2]贵州装备制造职业学院,贵州贵阳550025

出　　处：《合成化学》2024年第9期814-820,839,共8页Chinese Journal of Synthetic Chemistry

基　　金：国家地区基金资助项目(22361009)。

摘　　要：手性联吡啶配体和叔胺衍生的手性N-氧化物配体的合成是不对称催化领域研究的热点。本文以光学纯的各种取代脯氨酰胺(1)与联吡啶-6-甲醛(2)发生缩合环化反应,合成了8个未见文献报道的手性联吡啶叔胺3a~3h,收率75%~80%,dr>20∶1。化合物3在氧化剂m-CPBA(间氯过氧苯甲酸)的作用下发生氮原子上的氧化反应,合成了8个未见文献报道的手性联吡啶叔胺衍生的N-氧化物4a~4h,总产率45%~51%,dr>20∶1(4e为14/1)。化合物3和4结构经^(1)H NMR,^(13)C NMR和HR-MS(ESI-TOF)表征,化合物3h的绝对构型(3R,7aS)通过单晶X-射线衍射进一步进行了确定。手性联吡啶和手性N-氧化物作为优势配体,其骨架类化合物3和4的合成今后可以为不对称路易斯酸催化提供新配体筛选。The synthesis of chiral bipyridine ligands and chiral N-oxide ligands derived from tertiary amines remains an important topic in the field of asymmetric catalysis.In this paper,using optically pure various substituted prolamides(1)as the chiral source,the eight chiral bipyridine-tertiary amines 3a~3h were synthesized by condensation cyclization with bipyridyl-6-formaldehyde(2)in 75%~80%yield and dr>20/1.Then the nitrogen atom in the compounds(3)were oxidized under the action of chloro perbenzoic acid,an oxidant,to provide eight chiral bipyridine-tertiary amine-derived N-oxides 4a~4h in 45%~51%overall yield and dr 14/1~>20/1.The structures of products 3 and 4 were characterized by^(1)H NMR,^(13)C NMR and HR-MS(ESI-TOF).The absolute configuration(3R,7aS)of compound 3h was further determined by the single crystal X-ray diffraction.Chiral bipyridine and chiral N-oxide serve as privileged ligands,and the synthesis of their skeleton compounds 3 and 4 can provide new ligand screening for asymmetric Lewis acid catalysis in the future.

关 键 词：脯氨酰胺 联吡啶-6-甲醛 叔胺N-氧化物 手性配体 合成 

分 类 号：O626.13[理学—有机化学] O623.7[理学—化学]