通过揭示 Martin 的螺硅烷衍生的五配位甲硅烷基硅酸盐作为甲硅烷基自由基前体的反应性,揭示了可见光诱导的光催化 C-Si 形成策略。已经证明了广谱烯烃和炔烃的氢化硅烷化,以及杂芳烃的 C-H 硅烷化。值得注意的是,Martin 的螺硅烷非常稳定,可以通过简单的后处理过程回收。此外,使用水作为溶剂或低能量绿色 LED 作为替代能源,反应进行得很好。
Rhenium-mediated dehydrogenative silylation and highly regioselective hydrosilylation of nitrile substituted olefins
作者:Hailin Dong、Yanfeng Jiang、Heinz Berke
DOI:10.1016/j.jorganchem.2013.10.052
日期:2014.1
(I) complex [Re(CH3CN)3Br2(NO)] catalyzes the homogeneous hydrosilylation of a variety of substituted acrylonitriles, which were converted into the corresponding silyl-substituted alkanes with high regioselectivity of up to 94%. The products were analyzed by 1H NMR and GC–MS. A rhenium specific mechanism is proposed for the hydrosilylation of olefins.
complex(I)络合物[Re(CH 3 CN)3 Br 2(NO)]催化多种取代的丙烯腈的均相氢化硅烷化反应,这些丙烯腈被转化为相应的甲硅烷基取代的烷烃,具有高达94%的区域选择性。产物通过1 H NMR和GC-MS分析。提出了specific特异的机理用于烯烃的氢化硅烷化。
Highly Regioselective Rhenium-Catalyzed Hydrosilylation of Styrenes