The Synthesis of Primary Amines through Reductive Amination Employing an Iron Catalyst

Bäumler, Christoph; Bauer, Christof; Kempe, Rhett

doi:10.1002/cssc.202000856

Cited by 55 publications

(46 citation statements)

References 67 publications

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“… 43 − 47 Based on this concept, air-stable and reusable Ni-, Co-, and Fe-based catalysts for reductive amination reactions were developed ( Figure 1 a). 33 − 37 To date, there is no catalyst design strategy available to develop air-stable base metal catalysts for reductive aminations, except for the aforementioned “N-doping strategy,” and flammable ammonia gas and/or high H 2 pressures are still required to promote the amination reaction. Moreover, the active surface sites of these non-noble-metal catalysts are shielded due to encapsulation by N-doped carbon layers; thus, the stability of the NPs is achieved at the expense of their activity.…”

Section: Introductionmentioning

confidence: 99%

Single-Crystal Cobalt Phosphide Nanorods as a High-Performance Catalyst for Reductive Amination of Carbonyl Compounds

Sheng

Fujita

Yamaguchi

et al. 2021

JACS Au

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The development of metal phosphide catalysts for organic synthesis is still in its early stages. Herein, we report the successful synthesis of single-crystal cobalt phosphide nanorods (Co 2 P NRs) containing coordinatively unsaturated Co–Co active sites, which serve as a new class of air-stable, highly active, and reusable heterogeneous catalysts for the reductive amination of carbonyl compounds. The Co 2 P NR catalyst showed high activity for the transformation of a broad range of carbonyl compounds to their corresponding primary amines using an aqueous ammonia solution or ammonium acetate as a green amination reagent at 1 bar of H 2 pressure; these conditions are far milder than previously reported. The air stability and high activity of the Co 2 P NRs is noteworthy, as conventional Co catalysts are air-sensitive (pyrophorous) and show no activity for this transformation under mild conditions. P-alloying is therefore of considerable importance for nanoengineering air-stable and highly active non-noble-metal catalysts for organic synthesis.

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Section: Introductionmentioning

confidence: 99%

Single-Crystal Cobalt Phosphide Nanorods as a High-Performance Catalyst for Reductive Amination of Carbonyl Compounds

Sheng

Fujita

Yamaguchi

et al. 2021

JACS Au

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“…Our Co catalyst (Co/ N ‐SiC) was synthesized as shown in Figure 1 A. Firstly, we synthesized the N‐doped SiC support ( N ‐SiC), which contains 8 atom% (at %) nitrogen, as determined by elemental analysis, using a modified literature procedure [43, 44] . Secondly, the N ‐SiC material was wet impregnated with a solution of Co(NO 3 ) 2 in water.…”

Section: Methodsmentioning

confidence: 99%

General Synthesis of Secondary Alkylamines by Reductive Alkylation of Nitriles by Aldehydes and Ketones

Schönauer

Thomä

Kaiser

et al. 2020

Chemistry A European J

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The development of C−N bond formation reactions is highly desirable due to their importance in biology and chemistry. Recent progress in 3d metal catalysis is indicative of unique selectivity patterns that may permit solving challenges of chemical synthesis. We report here on a catalytic C−N bond formation reaction—the reductive alkylation of nitriles. Aldehydes or ketones and nitriles, all abundantly available and low‐cost starting materials, undergo a reductive coupling to form secondary alkylamines and inexpensive hydrogen is used as the reducing agent. The reaction has a very broad scope and many functional groups, including hydrogenation‐sensitive examples, are tolerated. We developed a novel cobalt catalyst, which is nanostructured, reusable, and easy to handle. The key seems the earth‐abundant metal in combination with a porous support material, N‐doped SiC, synthesized from acrylonitrile and a commercially available polycarbosilane.

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“…Surprisingly, with the ammonia dissolved in water, several ketones including aliphatic and heterocyclic as well as aldehydes were converted to the corresponding primary amines in good to excellent yield. Additionally, they also investigated the amination of pharmaceuticals, bioactive compounds, and natural products [27] . Undoubtedly, the heterogeneous Fe catalyst, especially the easily recoverable magnetically catalyst, which showed the high activity, stability, and excellent selectivity of reductive amination of bioactive compounds, opens an essential and promising application both in academia and industry.…”

Section: Earth‐abundant Transition Metalsmentioning

confidence: 99%

Earth‐abundant Metal‐catalyzed Reductive Amination: Recent Advances and Prospect for Future Catalysis

Liu

Song

2021

Chemistry An Asian Journal

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Nitrogen‐containing compounds, as an important class of chemicals, have been used widely in pharmaceuticals, materials synthesis. Transition metal‐catalyzed reductive amination of an aldehyde or a ketone with ammonia or an amine has been proved to be an efficient and practical method for the preparation of nitrogen‐containing compounds in academia and industry for a century. Given the above, several effective methods using transition metals have been developed in recent years. Noble transition metals like Pd, Pt, and Au‐based catalysts have been predominately used in reductive amination. Because of their high prices, strict official regulations of residues in pharmaceuticals, and deleterious effects on the biological system, their industrial applications are severely hampered. With the increasing sustainable and environmental problems, the Earth‐abundant transition metals including Ti, Fe, Co, Ni, and Zr have also been investigated for the reductive amination reaction and showed great potential to the advancement of sustainable and cost‐effective reductive amination processes. This critical review will mainly summarize the work using Earth‐abundant metals. The effects of different transition metals used in catalytic reduction amination were discussed and compared, and some suggestions were given. The last section highlights the catalytic activities of bi‐ and tri‐metallic catalysts. Indeed, this latter family is very promising and simultaneously benefits from increased stability, and selectivity, compared to monometallic NPs, due to synergistic substrate activation. Few comprehensive reviews focusing on Earth‐abundant transition metals catalyst has been published since 1948, although several authors reported some summaries dealing with one or the other part of this aspect. It is hoped that this critical review will inspire researchers to develop new efficient and selective earth‐abundant metal catalysts for highly, environmentally sustainable reductive amination methods, as well as improve the pharmaceutical industry and related chemical synthesis company traditional method with the utilization of the green method widely.

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The Synthesis of Primary Amines through Reductive Amination Employing an Iron Catalyst

Cited by 55 publications

References 67 publications

Single-Crystal Cobalt Phosphide Nanorods as a High-Performance Catalyst for Reductive Amination of Carbonyl Compounds

Single-Crystal Cobalt Phosphide Nanorods as a High-Performance Catalyst for Reductive Amination of Carbonyl Compounds

General Synthesis of Secondary Alkylamines by Reductive Alkylation of Nitriles by Aldehydes and Ketones

Earth‐abundant Metal‐catalyzed Reductive Amination: Recent Advances and Prospect for Future Catalysis

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