Synthesis of Symmetric and Unsymmetric Secondary Amines from the Ligand-Promoted Ruthenium-Catalyzed Deaminative Coupling Reaction of Primary Amines.
Synthesis of Symmetric and Unsymmetric Secondary Amines from the Ligand-Promoted Ruthenium-Catalyzed Deaminative Coupling Reaction of Primary Amines.
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DOI：
10.1021/acs.joc.8b00649
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发表时间：
2018-05-04
期刊：
影响因子：
--
通讯作者：
Yi CS
中科院分区：
文献类型：
--
作者：
Arachchige PTK;Lee H;Yi CS
四核Ru-H配合物与邻苯二酚配体（1/L1）原位生成的催化体系对两个伯胺直接脱氨偶联生成仲胺是有效的。催化剂1/L1具有高度的化学选择性，可促进两种不同伯胺的偶联生成不对称仲胺。苯胺与伯胺的类似偶联形成芳基取代仲胺。苯胺-d7经4-甲氧基苄胺处理后，偶联产物CH2上的氘掺入量显著（18% D）。4-甲氧基苄胺偶联反应产物α-碳的碳同位素效应最明显(C（1) = 1.015(2)）。通过测量4-甲氧基苯胺与一系列对取代苄胺4-X-C6H4CH2NH2 （X = OMe, Me， H， F, CF3）的偶联反应速率，构建了Hammett图。（ρ =−0.79±0.1）。在此基础上提出了一种合理的耦合反应机理方案。催化偶联方法提供了一种操作简单且具有化学选择性的仲胺产物合成方法，无需使用任何反应物或产生浪费的副产物。
The catalytic system generated in-situ from the tetranuclear Ru–H complex with a catechol ligand (1/L1) was found to be effective for the direct deaminative coupling of two primary amines to form secondary amines. The catalyst 1/L1 was highly chemoselective for promoting the coupling of two different primary amines to afford unsymmetric secondary amines. The analogous coupling of aniline with primary amines formed aryl-substituted secondary amines. The treatment of aniline-d7 with 4-methoxybenzylamine led to the coupling product with significant deuterium incorporation on CH2 (18% D). The most pronounced carbon isotope effect was observed on the α-carbon of the product isolated from the coupling reaction of 4-methoxybenzylamine (C(1) = 1.015(2)). Hammett plot was constructed from measuring the rates of the coupling reaction of 4-methoxyaniline with a series of para-substituted benzylamines 4-X-C6H4CH2NH2 (X = OMe, Me, H, F, CF3). (ρ = −0.79 ± 0.1). A plausible mechanistic scheme has been proposed for the coupling reaction on the basis of these results. The catalytic coupling method provides an operationally simple and chemoselective synthesis of secondary amine products without using any reactive reagents or forming wasteful byproducts.
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影响因子：
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作者：
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