SO42-/TiO2固体酸协同金鸡纳碱奎尼丁催化不对称Mannich反应

doi:10.6023/cjoc201507036

有机化学 ›› 2016, Vol. 36 ›› Issue (1): 196-201.DOI: 10.6023/cjoc201507036 上一篇下一篇

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SO₄^2-/TiO₂固体酸协同金鸡纳碱奎尼丁催化不对称Mannich反应

姚元勇, 舒华, 邢明明, 陈仕学, 卢忠英, 唐帮成

铜仁学院应用化学研究所材料与化学工程学院铜仁 554300

收稿日期:2015-07-28 修回日期:2015-09-10 发布日期:2015-09-17
通讯作者: 舒华, 唐帮成 E-mail:yyy0326.love@163.com
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 SO₄^2-/TiO₂ Cooperated with CinchonaAlkaloid Quinidine to Asymmetric Mannich Organocatalysis

Yao Yuanyong, Shu Hua, Xing Mingming, Chen Shixue, Lu Zhongying, Tang Bangcheng

Institute of Applied Chemistry, School of Material and Chemical Engineering, Tongren University, Tongren 554300

Received:2015-07-28 Revised:2015-09-10 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).

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1. SO₄^2-/TiO₂固体酸协同金鸡纳碱奎尼丁催化不对称Mannich反应.PDF(853KB)

摘要/Abstract

采用固体酸SO₄^2-/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SO₄^2-/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,SO₄^2-/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,SO₄^2-/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SO₄^2-/TiO₂, 金鸡纳碱奎尼丁

Via combination of solid acid SO₄^2-/TiO₂ with cinchona alkaloid quinidine (R), the chiral catalyst of SO₄^2-/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 SO₄^2-/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%.

Key words: β-amino esters, asymmetric Mannich organocatalysis, solid acid SO₄^2-/TiO₂, cinchona alkaloid quinidine

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姚元勇, 舒华, 邢明明, 陈仕学, 卢忠英, 唐帮成. SO₄^2-/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.

Yao Yuanyong, Shu Hua, Xing Mingming, Chen Shixue, Lu Zhongying, Tang Bangcheng. Utilization of Solid Acid SO₄^2-/TiO₂ Cooperated with CinchonaAlkaloid Quinidine to Asymmetric Mannich Organocatalysis[J]. Chin. J. Org. Chem., 2016, 36(1): 196-201.

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SO₄^2-/TiO₂固体酸协同金鸡纳碱奎尼丁催化不对称Mannich反应

Utilization of Solid Acid SO₄^2-/TiO₂ Cooperated with CinchonaAlkaloid Quinidine to Asymmetric Mannich Organocatalysis

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