Transition-Metal-Catalyzed Reductive Amination Employing Hydrogen

Chemical Reviews, Год журнала: 2020, Номер 120(17), С. 9583 - 9674

Опубликована: Авг. 19, 2020

The reductive amination, the reaction of an aldehyde or a ketone with ammonia amine in presence reducing agent and often catalyst, is important synthesis has been intensively investigated academia industry for century. Besides aldehydes, ketones, amines, starting materials have used that can be converted into (for instance, carboxylic acids organic carbonate nitriles) nitro compound) same catalyst. Mechanistically, starts condensation step during which carbonyl compound reacts amine, forming corresponding imine followed by reduction to alkyl product. Many these steps require catalyst activate agent. amination impressive regard product scope since primary, secondary, tertiary amines are accessible hydrogen most attractive agent, especially if large-scale formation issue, inexpensive abundantly available. Alkyl produced use fine bulk chemicals. They key functional groups many pharmaceuticals, agro chemicals, materials. In this review, we summarize work published on employing as No comprehensive review focusing subject 1948, albeit interesting summaries dealing one other aspect appeared. Impressive progress using catalysts based earth-abundant metals, nanostructured heterogeneous catalysts, made early development field recent years.

Язык: Английский

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Catalytic reductive aminations using molecular hydrogen for synthesis of different kinds of amines

Chemical Society Reviews, Год журнала: 2020, Номер 49(17), С. 6273 - 6328

Опубликована: Янв. 1, 2020

Reductive aminations constitute an important class of reactions widely applied in research laboratories and industries for the synthesis amines as well pharmaceuticals, agrochemicals biomolecules. In particular, catalytic reductive using molecular hydrogen are highly valued essential cost-effective sustainable production different kinds their functionalization. These couple easily accessible carbonyl compounds (aldehydes or ketones) with ammonia, nitro presence suitable catalysts that enable preparation linear branched primary, secondary tertiary including N-methylamines molecules used life science applications. general, represent valuable fine bulk chemicals, which serve key precursors central intermediates advanced molecules, dyes polymers. Noteworthily, amine functionalities present a large number biomolecules, play vital roles function these active compounds. challenging processes, especially syntheses primary amines, often non-selective suffer from over-alkylation reduction to corresponding alcohols. Hence, development perform efficient selective manner is crucial continues be attracts scientific interest. this regard, both homogeneous heterogeneous have successfully been developed access various amines. There need comprehensive review on discuss potential applicability methodology commercial, industrial medicinal importance. Consequently, we applications functionalized structurally diverse benzylic, heterocyclic aliphatic more complex drug targets. addition, mechanisms formation desired products possible side emphasized. This aims at communities working fields organic synthesis, catalysis, biological chemistry.

Язык: Английский

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Porous Silicon Carbide (SiC): A Chance for Improving Catalysts or Just Another Active-Phase Carrier?

Chemical Reviews, Год журнала: 2021, Номер 121(17), С. 10559 - 10665

Опубликована: Июль 13, 2021

There is an obvious gap between efforts dedicated to the control of chemicophysical and morphological properties catalyst active phases attention paid search new materials be employed as functional carriers in upgrading heterogeneous catalysts. Economic constraints common habits preparing catalysts have narrowed selection active-phase a handful materials: oxide-based ceramics (e.g. Al2O3, SiO2, TiO2, aluminosilicates-zeolites) carbon. However, these occasionally face that limit their application catalysis. For instance, oxides are easily corroded by acids or bases, carbon not resistant oxidation. Therefore, cannot recycled. Moreover, poor thermal conductivity metal oxide often translates into permanent alterations sites (i.e. sintering) compromise performance its lifetime on run. development for design synthesis advanced catalytic processes urgent priority catalysis future. Silicon carbide (SiC) non-oxide semiconductor with unique make it highly attractive several branches Accordingly, past decade has witnessed large increase reports SiC-based catalysts, also light steadily growing portfolio porous SiC covering wide range well-controlled pore structure surface properties. This review article provides comprehensive overview use macro/mesoporous catalysis, stressing features efficient, cost-effective, easy scale-up outlining success where other more classical supports failed. All applications will reviewed from perspective given chemical reaction, highlighting all improvements rising terms activity, selectivity, process sustainability. We feel experienced viewpoint producers end users (these authors) critical presentation help readership create own opinion central role future

Язык: Английский

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Tandem reductive amination and deuteration over a phosphorus-modified iron center

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Фев. 21, 2025

Deuterated amines are key building blocks for drug synthesis and the identification of metabolites new pharmaceuticals, which drives search general, efficient, widely applicable methods selective such compounds. Here, we describe a multifunctional phosphorus-doped carbon-supported Fe catalyst with highly dispersed isolated metal sites that allow tandem reductive amination-deuteration sequences. The optimal phosphorus-modified Fe-based shows excellent performance in terms both reactivity regioselectivity wide range deuterated anilines, amines, bioactive complexes, drugs (>50 examples). Experiments on gram scale recycling show application potential this method. Beyond direct applicability developed method, described approach opens perspective development single-atom catalysts other value-adding organic syntheses. play crucial role as identifying novel pharmaceuticals. This study introduces dual-functional iron efficiently enables amination deuteration one-pot process, utilizing H2 reducing agent cost-effective D2O deuterium source.

Язык: Английский

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Methanol as a Potential Hydrogen Source for Reduction Reactions Enabled by a Commercial Pt/C Catalyst

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(4), С. 2245 - 2259

Опубликована: Фев. 8, 2023

Catalytic reduction reactions using methanol as a transfer hydrogenating agent is gaining significant attention because this simple alcohol inexpensive and produced on bulk scale. Herein, we report the catalytic utilization of hydrogen source for different functional organic compounds such nitroarenes, olefins, carbonyl compounds. The key to success transformation use commercially available Pt/C catalyst, which enabled hydrogenation series functionalized nitroarenes-to-anilines, alkenes-to-alkanes, aldehydes-to-alcohols both solvent donor. practicability Pt-based protocol showcased by demonstrating catalyst recycling reusability well reaction upscaling. In addition, system was also adaptable N-methylation N-alkylation anilines via borrowing process. This work provides flexible approach prepare variety value-added products from readily methanol, Pt/C, other starting materials.

Язык: Английский

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

ChemSusChem, Год журнала: 2020, Номер 13(12), С. 3110 - 3114

Опубликована: Апрель 21, 2020

Abstract The reductive amination of ketones and aldehydes by ammonia is a highly attractive method for the synthesis primary amines. use catalysts, especially reusable based on earth‐abundant metals similarly appealing. Here, iron‐catalyzed amines through was realized. A broad scope very good tolerance functional groups were observed. Ketones, including purely aliphatic ones, aryl–alkyl, dialkyl, heterocyclic, as well could be converted smoothly into their corresponding In addition, pharmaceuticals, bioactive compounds, natural products demonstrated. Many groups, such hydroxy, methoxy, dioxol, sulfonyl, boronate ester substituents, tolerated. catalyst easy to handle, selective, dissolved in water employed nitrogen source. key specific Fe complex an N‐doped SiC material support.

Язык: Английский

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Facile and Efficient Synthesis of Primary Amines via Reductive Amination over a Ni/Al₂O₃ Catalyst

ACS Sustainable Chemistry & Engineering, Год журнала: 2021, Номер 9(21), С. 7318 - 7327

Опубликована: Май 19, 2021

The production of primary amines with high efficiency and selectivity employing appropriate catalysts is central importance yet challenging. Here, we reported Ni nanoparticles supported on γ-Al2O3 as a highly active heterogeneous catalyst for the synthesis through reductive amination in presence ammonia hydrogen. resulting Ni/Al2O3 exhibited outstanding performance selective carbonyl compounds (aldehydes ketones) involving aromatic, branched, purely aliphatic chemicals converted into their corresponding excellent yields (87∼99%) under mild reaction conditions (100 °C 2 MPa), which was attributed to synergistic effect strong metal–support interaction combined medium acidic sites. In particular, yield earth-abundant superior that precious metal (Ru, Rh, Pd), suggesting could be promising candidate industrial amines.

Язык: Английский

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

JACS Au, Год журнала: 2021, Номер 1(4), С. 501 - 507

Опубликована: Апрель 7, 2021

The development of metal phosphide catalysts for organic synthesis is still in its early stages. Herein, we report the successful single-crystal cobalt nanorods (Co2P NRs) containing coordinatively unsaturated Co–Co active sites, which serve as a new class air-stable, highly active, and reusable heterogeneous reductive amination carbonyl compounds. Co2P NR catalyst showed high activity transformation broad range compounds to their corresponding primary amines using an aqueous ammonia solution or ammonium acetate green reagent at 1 bar H2 pressure; these conditions are far milder than previously reported. air stability NRs noteworthy, conventional Co air-sensitive (pyrophorous) show no this under mild conditions. P-alloying therefore considerable importance nanoengineering air-stable non-noble-metal synthesis.

Язык: Английский

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Iron phosphide nanocrystals as an air-stable heterogeneous catalyst for liquid-phase nitrile hydrogenation

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Сен. 28, 2023

Iron-based heterogeneous catalysts are ideal metal owing to their abundance and low-toxicity. However, conventional iron nanoparticle exhibit extremely low activity in liquid-phase reactions lack air stability. Previous attempts encapsulate nanoparticles shell materials toward stability improvement were offset by the of nanoparticles. To overcome trade-off between catalysts, we developed air-stable phosphide nanocrystal catalysts. The exhibits high for nitrile hydrogenation, whereas demonstrate no activity. Furthermore, allows facile immobilization on appropriate supports, wherein TiO

Язык: Английский

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

Chemistry - An Asian Journal, Год журнала: 2021, Номер 16(17), С. 2371 - 2391

Опубликована: Июль 8, 2021

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

Язык: Английский

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