General synthesis of primary amines via reductive amination employing a reusable nickel catalyst
General synthesis of primary amines via reductive amination employing a reusable nickel catalyst
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DOI：
10.1038/s41929-018-0202-6
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发表时间：
2019-01-01
期刊：
影响因子：
37.8
通讯作者：
Kempe, R.
中科院分区：
文献类型：
--
作者：
Hahn, G.;Kunnas, P.;Kempe, R.
以地球上丰富的金属为基础的可重复使用的催化剂在有机合成中具有广泛的适用性，是更可持续地生产精细化学品、药品和农用化学品的关键。在这里，我们报道了一种纳米结构的镍催化剂，用于以溶于水的氨为原料，通过还原胺化反应合成伯胺。我们的催化剂在低温和压力下运行，具有高活性、可重复使用和易于操作的特点。从特定的镍络合物和伽马-Al_2O_3合成是简单的，这种络合物的配体-金属结合是关键。醛(包括纯脂肪族)、芳烷基、二烷基和二芳基酮都可以顺利地转化为伯胺。此外，还展示了药物、生物活性化合物和天然产物的胺化反应。许多官能团--包括对氢化敏感的例子--都是可以容忍的。我们希望我们的发现将激励其他人开发可重复使用的、富含稀土的纳米结构金属催化剂，用于复杂的有机转化。
Reusable catalysts based on earth-abundant metals with a broad applicability in organic synthesis are a key to a more sustainable production of fine chemicals, pharmaceuticals and agrochemicals. Herein, we report on a nanostructured nickel catalyst for the general and selective synthesis of primary amines via reductive amination, employing ammonia dissolved in water. Our catalyst, which operates at low temperature and pressure, is highly active, reusable and easy to handle. The synthesis from a specific nickel complex and gamma-Al2O3 is straightforward, with the ligand-metal combination of this complex being crucial. Aldehydes (including purely aliphatic ones), aryl-alkyl, dialkyl and diaryl ketones can all be converted smoothly into primary amines. In addition, the amination of pharmaceuticals, bioactive compounds and natural products is demonstrated. Many functional groups-including hydrogenation-sensitive examples-are tolerated. We expect that our findings will inspire others to develop reusable and nanostructured earth-abundant metal catalysts for complex organic transformations.