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

doi:10.6023/cjoc201302007

Chin. J. Org. Chem. ›› 2013, Vol. 33 ›› Issue (08): 1774-1781.DOI: 10.6023/cjoc201302007 Previous Articles Next Articles

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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

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 发布日期:2013-04-09
通讯作者: 聂永 E-mail:chm_niey@ujn.edu.cn
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.

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

School of Chemistry and Chemical Engineering, Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, University of Jinan, Jinan 250022

Received:2013-02-03 Revised:2013-03-10 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).

1. Copper(I)-Mediated Cross-Coupling Reaction of Carboranyl-lithium with Alkynyllithium：One-Pot Synthesis of C-Alkynyl-o-carboranes.PDF(1955KB)

Abstract

In the copper(I)-mediated homocoupling reaction of dilithio-o-carborane Li₂C₂B₁₀H₁₀at 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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Bian Deqian, Nie Yong, Miao Jinling, Wang Yafeng, Zhang Zhenwei. Copper(I)-Mediated Cross-Coupling Reaction of Carboranyl-lithium with Alkynyllithium：One-Pot Synthesis of C-Alkynyl-o-carboranes[J]. Chin. J. Org. Chem., 2013, 33(08): 1774-1781.

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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

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

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