辛可尼丁催化不对称吲哚与三氟丙酮酸乙酯的Friedel-Crafts烷基化反应  

Asymmetric Friedel-Crafts alkylation of indole with ethyl trifluoropyruvate catalyzed by cinchonidine

作　　者：于雪[1] 柯苗 张娟[1] 徐小娜 YU Xue;KE Miao;ZHANG Juan;XU Xiao-na(School of Pharmaceutical&Chemical Engineering,Xianyang Vocational Technical College,Xianyang 712000,China)

机构地区：[1]咸阳职业技术学院医药化工学院,陕西咸阳712000

出　　处：《化学工程师》2022年第11期14-18,共5页Chemical Engineer

基　　金：陕西省自然科学基础研究计划(面上)项目(2022JM-561);咸阳职业技术学院博士科研基金项目(No.2021BK01);咸阳职业技术学院科学研究基金资助项目(No.2020KJB02)。

摘　　要：本研究报道辛可尼丁催化不对称吲哚与三氟丙酮酸乙酯的Friedel-Crafts烷基化反应,合成得到手性3,3,3-三氟-2-羟基-2-(1H-吲哚-3-基)丙酸乙酯,产物结构经~1H NMR、C NMR和ESI-MS表征,产物对映体过量值(ee值)经手性高效液相色谱测定。并对影响产物收率及选择性的因素进行了考察,确定了最佳反应条件为:催化剂辛可尼丁用量为n(辛可尼丁))∶n(吲哚))=0.04∶1;反应溶剂为乙醚;反应温度-10℃;反应时间10h。在该条件下,产物3,3,3-三氟-2-羟基-2-(1H-吲哚-3-基)丙酸乙酯收率为93%,ee值为66.5%。Chiral ethyl 3,3,3-trifluoro-2-hydroxy-2-(1H-indol-3-yl)propanoate was synthesized by FriedelCrafts alkylation reaction of asymmetric indole with ethyl trifluoropyruvate catalyzed by cinchonidine,the structure of the product was characterized by~1H NMR,C NMR and ESI-MS.The enantiomeric excess(ee)of the product was determined by Chiral HPLC.The optimum reaction conditions were determined as follows:n∶n=0.04∶1,ether as solvent,reaction temperature is-10℃;reaction time is 10h.Under these reaction conditions,the yield of ethyl 3,3,3-trifluoro-2-hydroxy-2-(1H-indol-3-yl)propanoate was 93%and the ee value was up to66.5%.

关 键 词：金鸡纳碱 辛可尼丁 不对称催化 FRIEDEL-CRAFTS烷基化反应 

分 类 号：O621.34[理学—有机化学]