Hydrosilylation of Ketones, Imines and Nitriles Catalysed by Electrophilic Phosphonium Cations: Functional Group Selectivity and Mechanistic Considerations
作者:Manuel Pérez、Zheng-Wang Qu、Christopher B. Caputo、Vitali Podgorny、Lindsay J. Hounjet、Andreas Hansen、Roman Dobrovetsky、Stefan Grimme、Douglas W. Stephan
DOI:10.1002/chem.201406356
日期:2015.4.20
efficient hydrosilylation of ketones, imines and nitriles at room temperature. In the presence of this catalyst, adding one equivalent of hydrosilane to a nitrile yields a silylimine product, whereas adding a second equivalent produces the corresponding disilylamine. [(C6F5)3PCl][B(C6F5)4] and [(C6F5)3PBr][B(C6F5)4] are also synthesised and tested as catalysts. Competition experiments demonstrate that the
亲电子phospho盐,[(C 6 F 5)3 PF] [B(C 6 F 5)4 ],在室温下催化酮,亚胺和腈的有效氢化硅烷化。在这种催化剂的存在下,向腈中加入一当量的氢硅烷会产生甲硅烷基苯丙胺产物,而添加第二当量的甲硅烷会产生相应的二甲硅烷基胺。[(C 6 F 5)3 PCl] [B(C 6 F 5)4 ]和[(C 6 F 5)3 PBr] [B(C 6 F 5)4也被合成并作为催化剂测试。竞争实验表明,该反应对以下官能团表现出选择性,其优先顺序为:酮>腈>亚胺>烯烃。计算研究表明,该反应机理涉及通过与with中心的相互作用而使SiH键初始活化。然后,活化的络合物协同作用于不饱和底物上。