脲衍生物有机催化靛红与乙酰乙酸酯的不对称Aldol反应  

Organocatalyzed Enantioselective Aldol Reaction of Isatins and Acetoacetates

作　　者：穆宏文 杜楠 王黎明 金瑛 MU Hong-wen;DU Nan;WANG Li-ming;JIN Ying(Department of Pharmacy,Jilin Medical University,Jilin 132013,China;Department of Pharmacy,Yanbian University,Yanji 133000,China)

机构地区：[1]吉林医药学院药学院,吉林吉林132013 [2]延边大学药学院,吉林延吉133000

出　　处：《分子催化》2022年第1期51-57,共7页Journal of Molecular Catalysis(China)

基　　金：吉林省教育厅科学技术项目(JKH20200450KJ);吉林省卫生厅创新项目(2020J074);项目及大学生创新训练项目(S202113706053)资助

摘　　要：将Takemoto(硫)脲衍生物用于催化靛红与乙酰乙酸酯的不对称羟醛反应(Aldol).在0.1 mmol底物用量条件下,筛选出最佳催化剂体系为:5%(摩尔分数)催化剂N-[3,5-双(三氟甲基)苯基]-N′-[(1S,2S)-2-(二甲氨基)环己基]脲1b,1 mL甲基叔丁基醚为溶剂,0℃条件下反应.以76%~87%的产率和最高达87%的对映选择性获得了手性δ-(2-羟基吲哚-3基)-δ-羟基-β-酮酸酯.Takemoto′s(thio)urea derivatives were applied in the asymmetric direct Aldol reaction of isatins and acetoacetate.Under the condition of 0.1 mmol substrate amount,the optimized conditions were determined to be 5%(Mole fraction)loading catalyst N-[3,5-Bis(trifluoromethyl)phenyl]-N′-[(1S,2S)-2-(dimethylamino)cyclohexyl]urea(1b)in methyl tert-butyl ether(1 mL)at 0℃.The different substituted isatins were evaluated for the generality of this reaction,the desired chiral δ-(2-oxindole-3yl-)-δ-hydroxy-β-ketoesters bearing the were obtained in 76%~87%yield with up to 87%enantiomeric excess(ee).

关 键 词：(硫)脲衍生物 不对称催化 ALDOL反应 靛红 乙酰乙酸酯 

分 类 号：O621.251[理学—有机化学]