Development of a General Non-Noble Metal Catalyst for the Benign Amination of Alcohols with Amines and Ammonia

• Published in: Chemistry : a European journal 2013-03, Vol.19 (11), p.3665-3675
• Main Authors: Cui, Xinjiang, Dai, Xingchao, Deng, Youquan, Shi, Feng
• Format: Article
• Language: English
• Subjects: Alcohols; Alcohols - chemistry; Amination; Amines; Amines - chemical synthesis; Amines - chemistry; Ammonia; Ammonia - chemistry; Catalysis; Catalysts; Chemistry; Copper - chemistry; Diols; Ferric Compounds - chemistry; heterogeneous catalysis; Ligands; Magnetic properties; Molecular Structure; Nickel - chemistry; non-noble metals; Particle Size; Surface Properties; Synthesis
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201203417

The N‐alkylation of amines or ammonia with alcohols is a valuable route for the synthesis of N‐alkyl amines. However, as a potentially clean and economic choice for N‐alkyl amine synthesis, non‐noble metal catalysts with high activity and good selectivity are rarely reported. Normally, they are severely limited due to low activity and poor generality. Herein, a simple NiCuFeOx catalyst was designed and prepared for the N‐alkylation of ammonia or amines with alcohol or primary amines. N‐alkyl amines with various structures were successfully synthesized in moderate to excellent yields in the absence of organic ligands and bases. Typically, primary amines could be efficiently transformed into secondary amines and N‐heterocyclic compounds, and secondary amines could be N‐alkylated to synthesize tertiary amines. Note that primary and secondary amines could be produced through a one‐pot reaction of ammonia and alcohols. In addition to excellent catalytic performance, the catalyst itself possesses outstanding superiority, that is, it is air and moisture stable. Moreover, the magnetic property of this catalyst makes it easily separable from the reaction mixture and it could be recovered and reused for several runs without obvious deactivation. Non‐noble? No problem! A simple NiCuFeOx catalyst exhibits excellent activity and generality in selective alcohol amination with ammonia to produce many examples of primary or secondary amines, secondary aliphatic alcohol amination, diol amination, and alcohol amination with dimethylamine (see scheme).