One-pot, chemoselective synthesis of secondary amines from aryl nitriles using a PdPt–Fe₃O₄ nanoparticle catalyst

Abstract

<p>We have developed a new catalytic method for the one-pot, cascade synthesis of unsymmetrical secondary amines <italic>via</italic> the reductive amination of aryl nitriles with nitroalkanes using a PdPt–Fe₃O₄ nanoparticle (NP) catalyst.</p>

Nickel-catalyzed hydrogenative coupling of nitriles and amines for general amine synthesis

“…This process accelerates the preparation of diverse intermediates and chemical libraries for drug discovery ( 48 , 49 ). In this respect, nitrile-containing pharmaceuticals, agrochemicals, and biomolecules ( 26 ) can be selectively functionalized to even more valuable amines. Indeed, using our Ni-based protocol the cross coupling of cyhalofop-butyl, citalopram, and amino acid analogs, as well as AT1 angiotensin II receptor antagonist analog, febuxostat ester, letrozole, and anastrazole with amines and ammonia (Fig.…”

“…Hence the direct catalytic hydrogenation of nitriles to produce primary amines continues to attract attention for both academic and industrial synthesis (6)(7)(8)(9)(10). By contrast, the synthesis of diverse secondary and tertiary amines-including N-methylamines from nitriles-by cross coupling is highly challenging and does not typically proceed with high selectivity (25)(26)(27)(28)(29)(30). As shown in Fig.…”

Recent Advances in Chemical Modifications of Nitriles

“…[63] As a promising crystalline porous material, metal-organic frameworks (MOFs) are often employed as precursors to prepare transition alloy nanoparticles, which show high catalytic activity for the hydrogenation of nitriles. [12,13,64] Ni, Co and Ru supported on SiO 2 , [61] Pd supported on SiC, [65] Fe 3 O 4 [66] and other catalyst supports are also widely used in nitrile hydrogenation. In 2016, Li et al [64a] designed a bifunctional N-doped Co@C catalyst, Co@NC-900 73, which was prepared from pyrolyzing the N-containing CoÀ MOF at 900 °C.…”

Reduction of imines with a reusable bimetallic PdCo–Fe3O4catalyst at room temperature under atmospheric pressure of H2

“…This included the development of PdPt–Fe 3 O 4 NPs that have been employed in nitroarene reduction, 21 arylsilylation, 22 as well as secondary amine synthesis from benzonitriles and nitroarenes. 23 Additionally, AuPd–Fe 3 O 4 NP catalysts have been developed for reductive amination, 24 oxidation of furan-2,5-dimethylcarboxylate, 25 and N-formylation of secondary amines. 26 However, all these catalysts employed expensive, precious metals (Pd and Pt, Au and Pd) among the transition metal element group.…”