Experimental and computational studies on the C-H amination mechanism of tetrahydrocarbazoles via hydroperoxides.
Experimental and computational studies on the C-H amination mechanism of tetrahydrocarbazoles via hydroperoxides.
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四氢咔唑通过氢过氧化物的C-H胺化机理的实验和计算研究
DOI：
10.1002/chem.201405376
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
M. Klussmann
中科院分区：
文献类型：
--
作者：
N. Gulzar;K. M. Jones;H. Konnerth;M. Breugst;M. Klussmann
通过实验和计算研究了光化学生成的四氢咔唑过氧化氢与苯胺的酸催化反应，以确定其反应机理。动力学数据表明，过氧化氢的反应级数为1，苯胺的反应级数为0。使用密度泛函理论的计算研究支持实验结果，并预测最初生成的过氧化四氢咔唑的亚胺和烯胺亚基之间的初始互变异构化将是速率控制步骤。然后，烯胺互变异构体在质子化时失去过氧化氢，产生稳定的烯丙基碳正离子，该阳离子可逆地被溶剂或苯胺捕获，形成分离的产物。
The acid‐catalyzed reactions of photochemically generated tetrahydrocarbazole peroxides with anilines have been studied experimentally and computationally to identify the underlying reaction mechanism. The kinetic data indicate a reaction order of one in the hydroperoxide and zero in the aniline. Computational investigations using density functional theory support the experimental findings and predict an initial tautomerization between an imine and enamine substructure of the primarily generated tetrahydrocarbazole peroxide to be the rate controlling step. The enamine tautomer then loses hydrogen peroxide upon protonation, generating a stabilized allylic carbocation that is reversibly trapped by solvent or aniline to form the isolated products.