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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 被引量:3

Copper(I)-Mediated Cross-Coupling Reaction of Carboranyl-lithium with Alkynyllithium: One-Pot Synthesis of C-Alkynyl-o-carboranes
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摘要 室温下氯化亚铜参与的邻碳硼烷双锂盐Li2C2B10H10的白偶联反应,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-C2810H12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. 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 (intro- duced 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 devel- oped. It was found that the product distribution varied with the amount of n-BuLi and CuC1 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.
出处 《有机化学》 SCIE CAS CSCD 北大核心 2013年第8期1774-1781,共8页 Chinese Journal of Organic Chemistry
基金 国家自然科学基金(No.20702020) 山东省自然科学基金(No.ZR2010BM020)资助项目~~
关键词 碳硼烷 簇状化合物 有机锂 炔烃 交叉偶联 carborane cluster compounds organolithium alkynes cross-coupling
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