Iron‐Catalyzed Synthesis of Secondary Amines: On the Way to Green Reductive Aminations

Abstract

Amines represent important intermediates in chemical and biological processes. Herein, we describe the use of a nanostructured iron-based catalyst for the tandem reductive amination between nitroarenes and aldehydes using hydrogen as reductant. The nanostructured iron-catalyst is prepared by immobilization of an iron-phenanthroline complex onto a commercially available carbon support. In the reaction sequence a primary amine is formed in situ from the corresponding nitro compound. Reversible condensation with aldehydes forms the respective imines, which are finally reduced to the desired secondary amine. This synthesis of secondary amines is atom-economical and environmentally attractive using cheap and readily available organic compounds as starting materials.

Selective Hydrodeoxygenation of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Heterogeneous Iron Catalysts

“…However,t ot he best of our knowledge, the possibility of Fe-catalyzed HDO of HMF to DMF is still challenging. [49][50][51] Inspired by their work, we recently reported the efficient CTHo ff urfural to furfuryl alcohol over heterogeneous Fe catalysts. [46] Recently,nitrogen-doped carbon material-supportedFecatalysts have attracted much attention in some important chemical reactions sucha st he oxygen reduction reaction( ORR) or nitroarene hydrogenation.…”

Continuous Reductive Amination of Biomass‐Derived Molecules over Carbonized Filter Paper‐Supported FeNi Alloy

“…[4,8] In this case, however, the sustainabilityo ft he employed catalystb ecomes essential. [3] Alternatively,t he use of ac obalt-based catalysth as been reported. [9][10][11][12] The replacemento ft hese elements with inexpensive and abundant alternatives is highly desirable.…”

“…[3,19] Nitrobenzene was suggested as as ubstitute for anilines in reductivea mination.T his compound, commonlyu sed as ac heap feedstock [20] fort he synthesis of aromatic and primary amines by hydrogenations, undergoes ac ascadeo fr eactions, which commence with the quantitative reduction of the nitro group to afford the amine, which subsequently condenses with benzaldehydet op rovide the imine. Below the temperature threshold identified for each specific reaction, the only byproducto bserved in the reaction mixture was the corresponding unreactedi mine, which suggests the reduction of the latter wast he rate-limiting step.…”

Microwave-assisted hydroarylation of styrenes catalysed by transition metal oxide nanoparticles supported on mesoporous aluminosilicates

“…Among these transition metals, iron NPs have attracted a great interest in the design of environmentally friendly and effective catalysts as alternative to traditionally employed noble metal catalysts in several catalytic reactions. Fe-based systems have been proven to be the most effective and green system in modern organic synthesis because of their lower toxicity and easy accessibility [24,25].…”