奎宁衍生的新型手性胍催化剂的合成及其在不对称Michael加成反应中的应用研究  

Synthesis of Entryvel Chiral Guanidine OrgaEntrycatalysts from Quinine and Their Application in the Asymmetric Michacel Addition

作　　者：张露文 袁佳妮 何炜 ZHANG Lu-wen;YUAN Jia-ni;HE Wei(School of Pharmacy, Air Force Medical University, Xi’an 710000, China)

机构地区：[1]空军军医大学药学系,陕西西安710000

出　　处：《合成化学》2021年第2期85-90,共6页Chinese Journal of Synthetic Chemistry

基　　金：陕西省重点研发计划资助项目(2019ZDLSF03-03)。

摘　　要：以生物碱奎宁和不同胺为原料,通过4步反应合成了5种新型手性胍催化剂,其结构经^(1)H NMR,^(13)C NMR,IR和HR-MS(ESI)表征。探索了一系列奎宁衍生的手性胍催化剂催化硝基乙烯类化合物和硫代丙二酸酯的不对称Michael加成反应。通过优化反应条件,确定最佳条件为:5 mol%5e为催化剂,乙醚为溶剂,于20℃反应5 h。在此条件下进行了底物拓展,获得一系列2-(1-芳基-2硝基乙基)丙二酸二苯二硫酯,最高收率为92%,最高对映选择性为93%。Five Entryvel chiral guanidine catalysts were synthesized via a four-step reaction,using quinine and amines as starting materials.The structures were characterized by ^(1)H NMR,^(13)C NMR,IR and HR-MS(ESI).A series of chiral guanidine catalysts were applied to the asymmetric Michael addition reaction.The optimal conditions were confirmed as:5e as catalyst in ether at room temperature for 5 h.The substrate scope was explored,and the highest yield was 92%,and the highest enantioselectivity was 93%.

关 键 词：奎宁 手性胍 MICHAEL加成 手性硫脲 催化剂 合成 

分 类 号：O623.7[理学—有机化学] O623.6[理学—化学]