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N‐Silylation of Amines Mediated by Et3SiH/KOtBu
Helvetica Chimica Acta ( IF 1.8 ) Pub Date : 2019-11-28 , DOI: 10.1002/hlca.201900235
Fabrizio Palumbo 1 , Simon Rohrbach 1 , Tell Tuttle 1 , John A. Murphy 1
Affiliation  

Silylation of primary and secondary amines is reported, using triethylsilane as the silylating reagent in the presence of potassium tert‐butoxide (KOtBu). The reaction proceeds well in the presence of 0.2 equiv. of KOtBu. In competition experiments, aniline is selectively silylated over aliphatic amines. Computational studies support a catalytic mechanism which is initiated by KOtBu interacting with the silane to form KH and silylated amine. The KH then takes over the role of base in the propagation of the cyclic mechanism and deprotonates the amine. This reacts with R3SiH to afford the product R3SiNR′R′′ and regenerate KH.

中文翻译:

Et3SiH / KOtBu介导的胺的N-硅烷化

据报道,在丁醇钾(KO t Bu)存在下,使用三乙基硅烷作为甲硅烷基化试剂,使伯胺和仲胺甲硅烷基化。在0.2当量的存在下,反应进行得很好。的KO Ť卜。在竞争实验中,苯胺在脂肪胺上被选择性甲硅烷基化。计算研究支持一种催化机理,该机理是由KO t Bu与硅烷相互作用形成KH和甲硅烷基化胺而引发的。然后,KH在循环机理的传播中承担了碱的作用,并使胺脱质子。这与R 3 SiH反应以提供产物R 3 SiNR'R''并再生KH。
更新日期:2019-11-28
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