辛可宁-方酰胺催化剂的合成及应用  

Synthesis and Application of Cinchonine-squaramide Catalyst

作　　者：赵梅梅 杜漠 高艳蓉 唐文强 ZHAO Meimei;DU Mo;GAO Yanrong;TANG Wenqiang(Shaanxi Institute of International Trade&Commerce,Xi′an 712046,China;Collaborative Innovation Center of Green Manufacturing Technology for Traditional Chinese Medicine in Shaanxi Province,Xi′an 712046,China)

机构地区：[1]陕西国际商贸学院,陕西西安712046 [2]陕西省中药绿色制造技术协同创新中心,陕西西安712046

出　　处：《化学与生物工程》2023年第11期35-38,43,共5页Chemistry & Bioengineering

基　　金：陕西省教育厅2022年度专项科学研究计划项目(22JK0280),陕西国际商贸学院“中药药效物质研究”创新团队资助项目(SSY18TD02)。

摘　　要：以9-氨基-(9-脱氧)表辛可宁(2)和方酸二乙酯(3)为原料,经缩合反应得到一种结构新颖的辛可宁-方酰胺催化剂(1),并将其应用于催化β-硝基苯乙烯(4)和乙酰丙酮(5)的不对称Michael加成反应,得到手性3-(2-硝基-1-苯基乙基)戊-2,4-二酮(6),通过1HNMR、^(13)CNMR、MS等手段对辛可宁-方酰胺催化剂及催化产物6的结构进行了表征,并对催化产物6的合成条件进行了优化。结果表明,在辛可宁-方酰胺催化剂用量n(辛可宁-方酰胺催化剂)∶n(β-硝基苯乙烯)为0.08∶1、溶剂为二氯甲烷、室温下反应12 h的最佳条件下,催化产物6收率达到90%,ee值>99%。We synthesized a novel Cinchonine-squaramide catalyst(1)by condensation reaction of 9-amino-(9-deoxy)epicontinine(2)and diethyl squarate(3),and obtained chiral 3-(2-nitro-1-phenylethyl)pentyl-2,4-dione(6)through the asymmetric Michael addition reaction ofβ-nitrostyrene(4)and acetylacetone(5)catalyzed by Cinchonine-squaramide catalyst.Moreover,we characterized the structure of Cinchonine-squaramide catalyst and the catalytic product 6 by 1HNMR,^(13)CNMR,and MS,and optimized the synthetic conditions of the catalytic product 6.The results show that the yield of the catalytic product 6 can reach 90%,and the ee value is more than 99%under the optimum reaction conditions as follows:n(Cinchonine-squaramide catalyst)∶n(β-nitrostyrene)is 0.08∶1,dichloromethane is adopted as the solvent,and reaction time at room temperature is 12 h.

关 键 词：金鸡纳碱 辛可宁 方酰胺 不对称MICHAEL加成反应 

分 类 号：TQ215[化学工程—有机化工] O643.36[理学—物理化学]