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有机化学
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有机化学 ›› 2013, Vol. 33 ›› Issue (03): 558-561.DOI: 10.6023/cjoc201211028 上一篇    下一篇

研究论文

氢氧化铯催化端炔氢硒化: 高立体区域选择性合成(E)-1-芳硒基烯烃

王小勇a, 李治章a, 张卫军a, 王勰b, 陈锦杨b, 李宁波b, 邱仁华b, 许新华b   

  1. a 湖南科技学院生命科学与化工系 永州 425100;
    b 湖南大学化学化工学院 长沙 410082
  • 收稿日期:2012-11-15 修回日期:2012-12-11 发布日期:2012-12-13
  • 通讯作者: 李治章, 许新华 E-mail:xhx1581@yahoo.com.cn
  • 基金资助:

    湖南省自然科学基金(No. 11JJ2009)和国家自然科学基金(No. 21273068)资助项目.

Hydroselenation of Terminal Alkynes Catalyzed by Cesium Hydroxide: Highly Stereo- and Regio-selective Synthesis of (E)-1-Arylselenoalkenes

Wang Xiaoyonga, Li Zhizhanga, Zhang Weijuna, Wang Xieb, Chen Jinyangb, Li Ningbob, Qiu Renhuab, Xu Xinhuab   

  1. a Department of Life Science and Chemical Engineering, Hunan University of Science and Engineering, Yongzhou 425100;
    b College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082
  • Received:2012-11-15 Revised:2012-12-11 Published:2012-12-13
  • Supported by:

    Project supported by the Natural Science Foundation of Hunan Province (No. 11JJ2009) and the National Natural Science Foundation of China (No. 21273068).

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在催化量氢氧化铯存在下, 端炔与硒酚在N,N-二甲基甲酰胺(DMF)中、室温、氮气保护下, 发生亲核加成反应, 高收率、高立体选择性合成一系列(E)-1-芳硒基烯. 反应机理为氢氧化铯与硒酚反应产生的芳硒化铯, 随后对端炔进行亲核加成, 形成的烯基负离子水解得到产物. 这方法为不活泼端炔氢硒化提供了一条新的和简便途径.

关键词: 亲核加成, 立体选择性, 端炔, 氢硒化, 氢氧化铯, (E)-1芳硒基烯

In the presence of catalytic amount of cesium hydroxide, the hydroselenation of terminal alkynes occurred in N,N-dimethylformamide (DMF) at room temperature under nitrogen atmosphere to afford (E)-1-organseleno-1-alkene in high yields. The reaction mechanism is that selenols reacted with cesium hydroxide to give cesium selenides, which underwent nucleophilic addition to the alkynes to form selenium vinylic anion, hydrolyzed to give product (E)-1-organoselenovinylene and catalyst cesium hydroxide. The method could provide a new and expedient way for the hydroselenation of unactivated alkynes.

Key words: nucleophilic addition, regioselectivity, terminal alkyne, hydroselenolation, cesium hydroxide, (E)-1-organoseleno-1-alkene