CuOTf/NNN 三齿钳形配体催化不对称Henry 反应

doi:10.6023/cjoc1108303

有机化学 ›› 2012, Vol. 32 ›› Issue (06): 1131-1135.DOI: 10.6023/cjoc1108303 上一篇下一篇

研究简报

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).

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摘要/Abstract

以(R)-BINOL为原料合成NNN三齿钳形手性配体, 研究了其与各种金属盐形成金属络合物在室温下原位催化芳香醛与硝基甲烷的不对称Henry 反应. 考察了不同金属盐、溶剂、碱对反应的影响, 优化得到最佳反应条件为:CuOTf/NNN 三齿配体(1∶1)催化体系, 催化剂用量为10 mol%, 甲醇作溶剂, 室温反应5 d, 收率57%, 对映选择性80%ee; 加入10 mol%有机碱(Me₃Si)₂MeN 后反应速度加快, 对映选择性略有降低, 室温反应17 h, 收率37%, ee 值67%. 此催化体系适用于大部分的芳香醛, 收率中等, 对映选择性可达75% ee.

关键词: NNN 三齿钳形配体, 不对称Henry 反应, (R)-BINOL, 三氟甲磺酸亚铜

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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徐珊珊, 周宇涵, 曲景平. CuOTf/NNN 三齿钳形配体催化不对称Henry 反应[J]. 有机化学, 2012, 32(06): 1131-1135.

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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