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2013 , Vol. 33 >Issue 08: 1774 - 1781

DOI: https://doi.org/10.6023/cjoc201302007

研究论文

铜参与的碳硼烷锂盐与炔基锂的交叉偶联反应：“一锅法”合成C-炔基邻碳硼烷衍生物

  • 卞德乾 ,
  • 聂永 ,
  • 苗金玲 ,
  • 王亚峰 ,
  • 张振伟
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  • 济南大学化学化工学院 山东省氟化学化工材料重点实验室 济南 250022

收稿日期: 2013-02-03

  修回日期: 2013-03-10

  网络出版日期: 2013-04-09

基金资助

国家自然科学基金(No. 20702020)及山东省自然科学基金(No. ZR2010BM020)资助项目.

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Copper(I)-Mediated Cross-Coupling Reaction of Carboranyl-lithium with Alkynyllithium：One-Pot Synthesis of C-Alkynyl-o-carboranes

  • Bian Deqian ,
  • Nie Yong ,
  • Miao Jinling ,
  • Wang Yafeng ,
  • Zhang Zhenwei
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  • School of Chemistry and Chemical Engineering, Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, University of Jinan, Jinan 250022

Received date: 2013-02-03

  Revised date: 2013-03-10

  Online published: 2013-04-09

Supported by

Project supported by the National Natural Science Foundation of China (No. 20702020) and the Natural Science Foundation of Shandong Province (No. ZR2010BM020).

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摘要

室温下氯化亚铜参与的邻碳硼烷双锂盐Li2C2B10H10的自偶联反应, 除了生成预期产物联邻碳硼烷(2), 还生成少量由邻碳硼烷锂盐和(为邻碳硼烷o-C2B10H12锂化反应而引入的)过量丁基锂交叉偶联的产物1-丁基邻碳硼烷(4)和1,2-二丁基邻碳硼烷(5), 而氯化亚铜参与的邻碳硼烷、端炔、丁基锂的反应体系能够“一锅法”合成炔基邻碳硼烷(产率33～62%). 化合物5可由碳硼烷双锂盐与过量的1-溴丁烷反应获得(产率84.6%). 对化合物5与炔基碳硼烷衍生物通过核磁共振(1H, 13C, 11B)、红外光谱、质谱以及单晶X射线衍射(5)等手段进行了结构表征, 并对其可能的生成机理进行了探讨.

关键词： 碳硼烷; 簇状化合物; 有机锂; 炔烃; 交叉偶联

本文引用格式

卞德乾 , 聂永 , 苗金玲 , 王亚峰 , 张振伟 . 铜参与的碳硼烷锂盐与炔基锂的交叉偶联反应：“一锅法”合成C-炔基邻碳硼烷衍生物[J]. 有机化学, 2013 , 33(08) : 1774 -1781 . DOI: 10.6023/cjoc201302007

Abstract

In the copper(I)-mediated homocoupling reaction of dilithio-o-carborane Li2C2B10H10 at room temperature, the expected product 1,1'-bis(o-carborane) (2), the unexpected compounds 1-butyl-o-carborane (4) and 1,2-dibutyl-o-carborane (5) were obtained, the latter two being formed by the cross-coupling reaction of o-carboranyllithium with n-butyllithium (introduced for the lithiation of o-carborane C2B10H12). Based on this finding, the CuCl-mediated one-pot synthesis of C-alkynyl-o-carborane derivatives (yield 33%～62%) involving o-carborane, terminal alkynes and n-butyllithium was developed. It was found that the product distribution varied with the amount of n-BuLi and CuCl utilized. Compound 5 was separately prepared in a good yield (84.6%) via the reaction of dilithio-o-carborane with excess 1-bromobutane at reflux for 23 h. The structural characterization of compound 5 and the C-alkynyl-o-carboranes were carried out by means of NMR, IR, MS and single-crystal X-ray diffraction (5). The possible mechanism for the formation of the cross-coupling products is also discussed.

Key words： carborane; cluster compounds; organolithium; alkynes; cross-coupling

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