Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong , Shatin, New Territories, Hong Kong, China.
J Am Chem Soc. 2014 May 28;136(21):7599-602. doi: 10.1021/ja503489b. Epub 2014 May 16.
Zirconium/nickel comediated one-pot three-component cascade cyclization of carboryne, alkene, and 2-bromophenyltrimethylsilylacetylene has been achieved, leading to the formation of a series of C,C,B-substituted carborane-fused tricyclics. On the basis of experimental results, a plausible mechanism is proposed including [2 + 2 + 1] cross-cyclotrimerization followed by intramolecular direct selective cage B-C(sp(2)) coupling. This represents the first example of direct cage B-C(phenyl) coupling via cage B-H activation.
锆/镍介导的碳炔、烯烃和 2-溴苯基三甲基硅基乙炔的一锅法三组分级联环化反应已经实现，生成了一系列 C，C，B-取代的碳硼烷稠合三环化合物。基于实验结果，提出了一个合理的反应机理，包括[2+2+1]交叉环三聚反应，然后是分子内直接选择性笼 B-C(sp(2))偶联。这代表了通过笼 B-H 活化直接进行笼 B-C（苯基）偶联的首例实例。
