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Reductive amination using cobalt-based nanoparticles for synthesis of amines.
Nature Protocols ( IF 14.8 ) Pub Date : 2020-03-18 , DOI: 10.1038/s41596-019-0258-z
Kathiravan Murugesan 1 , Vishwas G Chandrashekhar 1 , Thirusangumurugan Senthamarai 1 , Rajenahally V Jagadeesh 1 , Matthias Beller 1
Affiliation  

Reductive aminations are an essential class of reactions widely applied for the preparation of different kinds of amines, as well as a number of pharmaceuticals and industrially relevant compounds. In such reactions, carbonyl compounds (aldehydes, ketones) react with ammonia or amines in the presence of a reducing agent and form corresponding amines. Common catalysts used for reductive aminations, especially for the synthesis of primary amines, are based on precious metals or Raney nickel. However, their drawbacks and limited applicability inspired us to look for alternative catalysts. The development of base-metal nanostructured catalysts is highly preferable and is crucial to the advancement of sustainable and cost-effective reductive amination processes. In this protocol, we describe the preparation of carbon-supported cobalt-based nanoparticles as efficient and practical catalysts for synthesis of different kinds of amines by reductive aminations. Template synthesis of a cobalt-triethylenediamine-terephthalic acid metal-organic framework on carbon and subsequent pyrolysis to remove the organic template resulted in the formation of supported single cobalt atoms and nanoparticles. Applying these catalysts, we have synthesized structurally diverse benzylic, aliphatic and heterocyclic primary, secondary and tertiary amines, including pharmaceutically relevant products, starting from inexpensive and easily accessible carbonyl compounds with ammonia, nitro compounds or amines and molecular hydrogen. To prepare this cobalt-based catalyst takes 26 h, and the reported catalytic reductive amination reactions can be carried out within 18-28 h.

中文翻译:

使用钴基纳米颗粒进行胺的还原胺化。

还原性胺化反应是一类重要的反应,广泛用于制备不同种类的胺以及许多药物和与工业相关的化合物。在这种反应中,羰基化合物(醛,酮)在还原剂的存在下与氨或胺反应并形成相应的胺。用于还原胺化,特别是用于合成伯胺的常用催化剂是基于贵金属或阮内镍。但是,它们的缺点和适用性有限促使我们寻找替代催化剂。贱金属纳米结构催化剂的开发是高度可取的,并且对可持续和成本有效的还原胺化工艺的发展至关重要。在这个协议中 我们描述了碳负载的钴基纳米颗粒的制备,作为通过还原胺化合成不同种类胺的有效而实用的催化剂。碳上的钴-三亚乙基二胺-对苯二甲酸金属-有机骨架的模板合成,以及随后的热解以去除有机模板,导致形成了负载的单个钴原子和纳米颗粒。使用这些催化剂,我们从廉价且易于获得的羰基化合物与氨,硝基化合物或胺以及分子氢开始,合成了结构多样的苄基,脂肪族和杂环伯,仲和叔胺,包括药学上相关的产品。制备这种钴基催化剂需要26个小时,
更新日期:2020-03-18
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