SO42-/TiO2固体酸协同金鸡纳碱奎尼丁催化不对称Mannich反应
收稿日期: 2015-07-28
修回日期: 2015-09-10
网络出版日期: 2015-09-17
基金资助
贵州省教育厅自然科学“青年”基金(No. KY(2014)317 )和贵州省教育厅自然科学“联合”基金(No. KY(2012)069)资助项目.
Utilization of Solid Acid SO42-/TiO2 Cooperated with CinchonaAlkaloid Quinidine to Asymmetric Mannich Organocatalysis
Received date: 2015-07-28
Revised date: 2015-09-10
Online published: 2015-09-17
Supported by
Project supported by the Youth Foundation of Guizhou Educational Ministry Science and Technology (No. KY (2014)317)} and the Foundation of Guizhou Educational Ministry Science and Technology (No. KY(2012)069).
采用固体酸SO42-/TiO2与金鸡纳碱奎尼丁[Quinidine (R)]进行负载, 制备出具有较强氢键供体的SO42-/TiO2/Quinidine (R)手性催化剂, 并对比了金鸡纳碱奎尼丁及其衍生物金鸡纳碱奎尼丁-硫脲在不对称Mannich有机催化中的催化活性. 实验结果显示: 在相同的催化条件下,SO42-/TiO2/quinidine (R)在不对称Mannich催化反应的催化活性性能高于金鸡纳碱奎尼丁, 低于金鸡纳碱奎尼丁-硫脲. 同时, 通过催化条件优化,SO42-/TiO2/quinidine (R)催化剂在间二甲苯为溶剂、－40 ℃及搅拌72 h的催化条件下, 可获得具有较高光学活性的手性β-氨基酸酯类衍生物(89%～95% ee).
关键词： β-氨基酸酯; 不对称Mannich有机催化; 固体酸SO42-/TiO2; 金鸡纳碱奎尼丁
姚元勇 , 舒华 , 邢明明 , 陈仕学 , 卢忠英 , 唐帮成 . SO42-/TiO2固体酸协同金鸡纳碱奎尼丁催化不对称Mannich反应[J]. 有机化学, 2016 , 36(1) : 196 -201 . DOI: 10.6023/cjoc201507036
Via combination of solid acid SO42-/TiO2 with cinchona alkaloid quinidine (R), the chiral catalyst of SO42-/TiO2/quinidine (R) carrying strong hydrogen-bonding donor has been obtained, which was evaluated on catalytic activity in the asymmetric organocatalysis, as comparing with quinidine (R) and thiourea-quinidine (R) derived from cinchona alkaloids. The result obviously showed that under the same conditions, the catalytic activity of SO42-/TiO2/quinidine (R) is more than that of quinidine (R), but less than that of thiourea-quinidine (R). Simultaneously, chiral β-amino ester derivatives with high optical activities were afforded under the optimum conditions of m-xylene as solvent and stirring for 72 h at －40 ℃. The value of ee was allowed to be the range of 89%～95%.
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