Asymmetric Henry Reaction Catalyzed by CuOTf/NNN Tridentate Pincer Ligand

doi:10.6023/cjoc1108303

Chin. J. Org. Chem. ›› 2012, Vol. 32 ›› Issue (06): 1131-1135.DOI: 10.6023/cjoc1108303 Previous Articles Next Articles

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CuOTf/NNN 三齿钳形配体催化不对称Henry 反应

徐珊珊, 周宇涵, 曲景平

大连理工大学制药科学与技术学院精细化工国家重点实验室大连 116024

收稿日期:2011-08-30 修回日期:2012-02-08 发布日期:2012-02-21
通讯作者: 周宇涵, 曲景平 E-mail:zhouyh@dl.cn; qujp@dlut.edu.cn
基金资助:
中央高校基本科研业务费专项资金(No. DUT10LK41)资助项目.

Asymmetric Henry Reaction Catalyzed by CuOTf/NNN Tridentate Pincer Ligand

Xu Shanshan, Zhou Yuhan, Qu Jingping

State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024

Received:2011-08-30 Revised:2012-02-08 Published:2012-02-21
Supported by:
Project supported by the Fundamental Research Funds for the Central Universities (No. DUT10LK41).

The NNN tridentate pincer chiral ligand was synthesized from (R)-BINOL to combine with a series of metal salts to catalyze asymmetric Henry reaction in situ at room temperature. The system of CuOTf/NNN ligand (1∶1) was proved to be potential catalyst in Henry reaction of 4-nitrobenzaldehyde with nitromethane. Various solvents and bases were surveyed for the reaction subsequently. When the loading of catalyst was 10 mol%, it showed catalytic efficiency for the reaction in methanol with 80% enantiomeric excess. With the assistance of (Me₃Si)₂NMe, the reaction was accelerated although enantiomeric excess was decreased to 67% ee. In addition, the catalyst showed moderate catalytic efficiency for Henry reaction between a variety of benzaldehydes and nitromethane to afford the expected products in moderate yields with good enantioselectivities (up to 75% ee).

Key words: NNN tridentate pincer ligand, asymmetric Henry reaction, (R)-BINOL, CuOTf

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Xu Shanshan, Zhou Yuhan, Qu Jingping. Asymmetric Henry Reaction Catalyzed by CuOTf/NNN Tridentate Pincer Ligand[J]. Chin. J. Org. Chem., 2012, 32(06): 1131-1135.

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CuOTf/NNN 三齿钳形配体催化不对称Henry 反应

Asymmetric Henry Reaction Catalyzed by CuOTf/NNN Tridentate Pincer Ligand

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