Transition-Metal-Catalyzed Reductive Amination Employing Hydrogen

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(17), P. 9583 - 9674

Published: Aug. 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.

Language: Английский

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

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(17), P. 6273 - 6328

Published: Jan. 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.

Language: Английский

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Highly selective and robust single-atom catalyst Ru1/NC for reductive amination of aldehydes/ketones

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: June 2, 2021

Abstract Single-atom catalysts (SACs) have emerged as a frontier in heterogeneous catalysis due to the well-defined active site structure and maximized metal atom utilization. Nevertheless, robustness of SACs remains critical concern for practical applications. Herein, we report highly active, selective robust Ru SAC which was synthesized by pyrolysis ruthenium acetylacetonate N/C precursors at 900 °C N 2 followed treatment 800 NH 3 . The resultant 1 -N exhibits moderate capability hydrogen activation even excess , enables effective modulation between transimination hydrogenation activity reductive amination aldehydes/ketones towards primary amines. As consequence, it shows superior amine productivity, unrivalled resistance against CO sulfur, unexpectedly high stability under harsh hydrotreating conditions compared most nanocatalysts. This strategy will open an avenue rational design other demanding transformations.

Language: Английский

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Functional Mesoporous Silica Nanomaterials for Catalysis and Environmental Applications

Bulletin of the Chemical Society of Japan, Journal Year: 2020, Volume and Issue: 93(12), P. 1459 - 1496

Published: July 22, 2020

Abstract Silica materials are used in a wide range of applications such as catalysis, photocatalysis, CO2 capture, and environmental remediation. These nanomaterials (NMs) have been extensively investigated since the advent Stöber silica. However, absence pores small surface area silica limits its applications. Later, discovery MCM-41 type mesoporous using surfactants structural directing agents became revolutionary field NMs. This review focuses on methods for synthesizing (NMs), especially nanoparticles (NPs), their various fields including catalysis (i.e., support nanoparticle catalysts) remediation (CO to conversion, volatile organic compound (VOC) removal, capture). The current issues/challenges realizing practical these conventional also highlighted. compares characteristics MCM-41, SBA-15, KCC-1 demonstrate effect morphology pore architecture properties silica-based scope future developments synthesis with different sizes morphologies is discussed.

Language: Английский

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Quasi Pd1Ni single-atom surface alloy catalyst enables hydrogenation of nitriles to secondary amines

Nature Communications, Journal Year: 2019, Volume and Issue: 10(1)

Published: Nov. 1, 2019

Hydrogenation of nitriles represents as an atom-economic route to synthesize amines, crucial building blocks in fine chemicals. However, high redox potentials render this approach produce a mixture imines and low-value hydrogenolysis byproducts general. Here we show that quasi atomic-dispersion Pd within the outermost layer Ni nanoparticles form Pd1Ni single-atom surface alloy structure maximizes utilization breaks strong metal-selectivity relations benzonitrile hydrogenation, by prompting yield dibenzylamine drastically from ∼5 97% under mild conditions (80 °C; 0.6 MPa), boosting activity about eight four times higher than Pt standard catalysts, respectively. More importantly, undesired carcinogenic toluene by-product is completely prohibited, rendering its practical applications, especially pharmaceutical industry. Such strategy can be extended broad scope with yields secondary amines conditions.

Language: Английский

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Organonitrogen Chemicals from Oxygen-Containing Feedstock over Heterogeneous Catalysts

ACS Catalysis, Journal Year: 2019, Volume and Issue: 10(1), P. 311 - 335

Published: Nov. 25, 2019

Organonitrogen chemicals, such as amines, nitriles, amides, amino acids, and N-heterocycles, are ubiquitous building blocks in chemical industry. Conventional methodologies to prepare these however, suffer from using toxic, corrosive starting materials and/or employing harsh reaction conditions. Recent advances suggest that heterogeneous catalysts promising promote the formation of organonitrogen chemicals cheap abundant materials. In this Review, we summarize most recent developments supported solid make oxygen-containing feedstock NH3. We introduce four key transformations including carbonyls/alcohols alcohols/carbonyls alcohols/nitriles N-heterocycles. each section, function catalyst structure–activity correlations discussed. Auxiliary factors affecting performance catalysts, solvent effect, substituent group reactor design also reviewed.

Language: Английский

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Synergistic catalysis on Fe–N_x sites and Fe nanoparticles for efficient synthesis of quinolines and quinazolinones via oxidative coupling of amines and aldehydes

Chemical Science, Journal Year: 2019, Volume and Issue: 10(44), P. 10283 - 10289

Published: Jan. 1, 2019

A heterogeneous nanocomposite of Fe–Fe₃C nanoparticles and Fe–N_x sites on N-doped porous carbon allows for efficient synthesis quinolines quinazolinones via oxidative coupling amines aldehydes in aq. solution using H₂O₂ as the oxidant.

Language: Английский

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Ambient-Temperature Synthesis of Primary Amines via Reductive Amination of Carbonyl Compounds

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(14), P. 7763 - 7772

Published: June 16, 2020

Efficient synthesis of primary amines via low-temperature reductive amination carbonyl compounds using NH3 and H2 as the nitrogen hydrogen resources is highly desired challenging in chemistry community. Herein, we employed naturally occurring phytic acid a renewable precursor to fabricate titanium phosphate (TiP)-supported Ru nanocatalysts with different reduction degrees RuO2 (Ru/TiP-x, x represents temperature) by combining ball milling molten-salt processes. Very interestingly, obtained Ru/TiP-100 had good catalytic performance for at ambient temperature, resulting from synergistic cooperation support (TiP) Ru/RuO2 suitable proportion Ru0 (52%). Various could be efficiently converted into corresponding high yields. More importantly, conversion other substrates reducible groups also achieved temperature. Detailed investigations indicated that partially reduced were indispensable. The activity selectivity catalyst originates relatively acidity electron density metallic Ru0.

Language: Английский

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A decennary update on applications of metal nanoparticles (MNPs) in the synthesis of nitrogen- and oxygen-containing heterocyclic scaffolds

RSC Advances, Journal Year: 2020, Volume and Issue: 10(54), P. 32740 - 32820

Published: Jan. 1, 2020

Metal nanoparticle (MNP)-catalyzed synthesis of nitrogen- and oxygen-containing heterocyclic scaffolds.

Language: Английский

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

ACS Sustainable Chemistry & Engineering, Journal Year: 2021, Volume and Issue: 9(21), P. 7318 - 7327

Published: May 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.

Language: Английский

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