有机催化苯并三氮唑与查耳酮的不对称aza-Michael加成反应  

Organocatalytic Asymmetric Aza-Michael Reaction of Benzotriazole with Chalcones

作　　者：王黎明 熊蕊 穆宏文 金瑛 WANG Li-Ming;XIONG Rui;MU Hong-wen;JIN Ying(Department of Pharmacy,Jilin Medical University,Jilin 132013,China)

机构地区：[1]吉林医药学院药学院

出　　处：《化学试剂》2018年第8期775-778,800,共5页Chemical Reagents

基　　金：国家自然科学基金资助项目(21102055);吉林省教育厅“十三五”科学技术项目(JJKH20170409KJ);吉林省卫生厅创新项目(2017J104);大学生创新创业训练计划项目(201746)

摘　　要：将脯氨醇衍生物用于有机催化苯并三氮唑与查耳酮的不对称aza-Michael加成反应,制备手性氮杂环化合物。通过^1HNMR、^13CNMR和HR-MS光谱技术对其结构进行表征,通过HPLC手性色谱柱测定产品的对映体过量值（e.e.）。考察溶剂、温度及催化剂用量对反应立体选择性的影响,进而优化催化剂体系。结果表明,最佳催化条件为20 mol%催化剂,甲苯为溶剂,0℃下反应。将此条件用于7种不同取代查耳酮的反应,得到了58%-70%的收率和最高达72%的对映选择性,拓宽了该反应的催化剂类型和底物范围。Prolinol derivatives as organocatalysts were applied in asymmetric aza-Michael addition reaction of benzotriazole with different chalcones to prepare chiral N-heterocycles.The structure of compounds were confirmed by ^1 HNMR,^13 CNMR and HR-MS and the enantioselectivities of adducts were determined by HPLC chiral column. The effect of solvent,temperature and catalyst loading ammount were investigated.The optimized conditions were confirmed including toluene as the solvent with a 20 mol% loading of catalyst at 0 ℃. The seven different desired products were obtained in 58% - 70% yield with up to 72% e. e under the screened catalysis condition.The catalyst type and the substrate scope were broadened in this methodology.

关 键 词：脯氨醇衍生物 不对称催化 aza-Michael加成反应 苯并三氮唑 查耳酮 

分 类 号：O621.3[理学—有机化学]