Kuai Chang-Sheng, Ji Ding-Wei, Zhao Chao-Yang, Liu Heng, Hu Yan-Cheng, Chen Qing-An
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China.
Angew Chem Int Ed Engl. 2020 Oct 19;59(43):19115-19120. doi: 10.1002/anie.202007930. Epub 2020 Aug 20.
A method for the regiodivergent and stereoselective hydrosilylation of the basic industrial feedstock isoprene with unactivated silanes has been developed using earth-abundant iron catalysts. The manipulation of regioselectivity relies on fine modification of the coordination geometry of the iron center. While a bidentate pyridine imine ligand promoted the formation of allylic silanes through 4,1-addition, selectivity for the 3,4-adduct homoallylic silanes was observed with a tridentate nitrogen ligand. Experimental studies and analysis were carried out to elucidate the reaction mechanism and the factors enabling manipulation of the regioselectivity. This study contributes to the art of regioselectivity control in alkene hydrofunctionalization.
利用储量丰富的铁催化剂，已开发出一种将基础工业原料异戊二烯与未活化硅烷进行区域发散性和立体选择性硅氢化反应的方法。区域选择性的控制依赖于对铁中心配位几何结构的精细修饰。当双齿吡啶亚胺配体通过1,4-加成促进烯丙基硅烷的形成时，使用三齿氮配体则观察到对1,3-加成产物高烯丙基硅烷的选择性。开展了实验研究与分析，以阐明反应机理以及实现区域选择性控制的因素。这项研究为烯烃氢官能化反应中区域选择性控制技术做出了贡献。
