Substituent Effects on Stoichiometric and Catalytic Cleavage of Carbon-Nitrogen Bonds in Aniline Derivatives by Ruthenium-Phosphine Complexes
Substituent Effects on Stoichiometric and Catalytic Cleavage of Carbon-Nitrogen Bonds in Aniline Derivatives by Ruthenium-Phosphine Complexes
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DOI：
10.1021/om3011855
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发表时间：
2013-01-28
期刊：
影响因子：
2.8
通讯作者：
Kakiuchi, Fumitoshi
中科院分区：
文献类型：
--
作者：
Koreeda, Tetsuro;Kochi, Takuya;Kakiuchi, Fumitoshi
考察了不同邻酰基苯胺衍生物与Ru配合物的反应活性。邻酰基苯胺与RuH_2(CO)(PPh_3)(3)(1)或“Ru(CO)(PPh_3)(3)”(4)反应生成N-H和C-N键断裂形成的氨基氢化物3和芳基氨基络合物6。添加烯烃，如乙烯基硅烷，会加速C-N键的断裂。芳基酰胺络合物6与芳基硼酸盐反应时可提供C-N芳基化产物。通过竞争实验考察了含有不同取代基的邻酰基苯胺的相对反应性，发现给电子取代基增加了化学计量反应和催化反应中C-N键断裂的相对易度。这里观察到的趋势与以前报道的钽介导的C-N键断裂的趋势不同。
The reactivity of various o-acylaniline derivatives with ruthenium complexes was examined. The reaction of o-acylanilines with RuH2(CO)(PPh3)(3) (1) or an activated ruthenium species formulated as "Ru(CO)(PPh3)(3)" (4) gave amido hydrido complexes 3 and aryl amido complexes 6 formed via N-H and C-N bond cleavage, respectively. Addition of olefins, such as vinylsilanes, accelerates the C-N bond cleavage. The aryl amido complexes 6 can provide the C-N arylation product upon treatment with arylboronates. The relative reactivity of o-acylanilines bearing various substituents was investigated by competition experiments, and it was found that electron-donating substituents increase the relative facileness of the C-N bond cleavage in both stoichiometric and catalytic reactions. The trend observed here is different from the one observed for the previously reported tantalum-mediated C-N bond cleavage.