Mn-Catalyzed Aromatic C-H Alkenylation with Terminal Alkynes
Mn-Catalyzed Aromatic C-H Alkenylation with Terminal Alkynes
复制标题
Mn 催化末端炔烃芳香族 C-H 烯基化
DOI：
10.1021/ja311689k
复制
发表时间：
2013-01-30
影响因子：
15
通讯作者：
Wang, Congyang
中科院分区：
文献类型：
--
作者：
Zhou, Bingwei;Chen, Hui;Wang, Congyang
首次报道了锰催化的芳香族C-H链烯基化反应。该方法的特点是操作简单的催化剂体系，含有市售的MnBr（CO）5和二环己基胺（Cy 2NH）。该反应以高度化学选择性、区域选择性和立体选择性的方式容易地发生，以高产率递送反马氏E-构型的烯烃。实验研究和密度泛函理论计算表明：（1）该反应是由锰和碱协同作用的C-H活化步骤引发的;（2）锰配体和炔基锰物种是反应的关键中间体;（3）配体间的氢转移和炔基辅助的C-H活化是锰催化该反应的关键步骤。
The first manganese-catalyzed aromatic C-H alkenylation with terminal alkynes is described. The procedure features an operationally simple catalyst system containing commercially available MnBr(CO)5 and dicyclohexylamine (Cy2NH). The reaction occurs readily in a highly chemo-, regio-, and stereoselective manner delivering anti-Markovnikov E-configured olefins in high yields. Experimental study and DFT calculations reveal that (1) the reaction is initiated by a C-H activation step via the cooperation of manganese and base; (2) manganacycle and alkynylmanganese species are the key reaction intermediates; and (3) the ligand-to-ligand H-transfer and alkynyl-assisted C-H activation are the key steps rendering the reaction catalytic in manganese.