有机催化4-羟基香豆素与靛红、丙二腈的不对称Michael加成/环化串联反应  

Organocatalytic enantioselective Michael/cyclization tandem reaction of 4-hydroxycoumarin with isatin and malononitrile

作　　者：孙玉虹 顾盈盈 王黎明 金瑛 SUN Yu-hong;CU Ying-ying;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：《化学研究与应用》2024年第9期2073-2079,共7页Chemical Research and Application

基　　金：吉林省科技厅自然科学基金项目(20230101226JC)资助;吉林省教育厅科学技术项目(JJKH20240595KJ)资助;国家级大学生创新创业训练计划项目(202313706020)资助。

摘　　要：含有杂环的光学活性螺环羟吲哚衍生物因其多种多样的生物活性而备受关注。靛红衍生物的不对称Michael/环化串联反应是构建手性螺环羟吲哚化合物的重要方法。本文将11种有机催化剂用于靛红、4-羟基香豆素与丙二腈的不对称Michael加成/环化串联反应。筛选出最佳的催化剂体系为:10 mol%金鸡纳碱衍生物催化剂1f,二氯甲烷(1 m L)为溶剂,室温反应。将最佳条件用于不同取代靛红的反应,以80~88%的产率和最高达96%的对映选择性获得了螺[羟吲哚-3,4′-吡喃色烯]化合物。本研究拓宽了该反应的催化剂类型和底物范围。Optically active spirooxindoles containing heterocycle have attracted much attention due to their diverse biological activi-ties.The asymmetric Michael/cyclization tandem reaction of isatin derivatives is an important method for constructing chiral spiroox-indoles.11 Organocatalysts were applied in the asymmetric Michael/cyclization reaction of isatins,malononitrile and 4-hydroxycou-marin.The optimized conditions were determined to be 10 mol%loading cinchona alkaloid derivative 1f in CH2Cl2(1 mL)at room temperature.The substituted isatins were evaluated to explore the general applicability of this reaction,the desired chiral spiro[oxin-dole-3,4'-pyranochromene]derivatives were obtained in 80~88%yield with up to 96%enantiomeric excess(ee).The catalyst type and the substrate scope were broadened in this methodology.

关 键 词：金鸡纳碱衍生物 有机催化 不对称Michael加成/环化串联反应 4-羟基香豆素 靛红 

分 类 号：O625.2[理学—有机化学]