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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Graphitic phosphorus coordinated single Fe atoms for hydrogenative transformations

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: Aug. 13, 2020

Abstract Single-atom metal-nitrogen-carbon (M-N-C) catalysts have sparked intensive interests, however, the development of an atomically dispersed metal-phosphorus-carbon (M-P-C) catalyst has not been achieved, although molecular metal-phosphine complexes found tremendous applications in homogeneous catalysis. Herein, we successfully construct graphitic phosphorus species coordinated single-atom Fe on P-doped carbon, which display outstanding catalytic performance and reaction generality heterogeneous hydrogenation N-heterocycles, functionalized nitroarenes, reductive amination reactions, while corresponding atoms embedded N-doped carbon are almost inactive under same conditions. Furthermore, find that activity sharply decreased when were transformed to clusters/nanoparticles by post-impregnation species. This work can be fundamental interest for design utilizing P as coordination sites well practical use application M-P-C

Language: Английский

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Electrochemical C–N coupling of CO₂and nitrogenous small molecules for the electrosynthesis of organonitrogen compounds

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(6), P. 2193 - 2237

Published: Jan. 1, 2023

Electrochemical C–N coupling reaction by renewable electricity for the electrosynthesis of organonitrogen compounds with abundant CO 2 and nitrogenous small molecules as carbon nitrogen sources, respectively, is a promising sustainable synthetic strategy.

Language: Английский

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Sustainable access to renewable N-containing chemicals from reductive amination of biomass-derived platform compounds

Green Chemistry, Journal Year: 2020, Volume and Issue: 22(20), P. 6714 - 6747

Published: Jan. 1, 2020

The latest studies in synthesis of nitrogen-containing compounds from various bio-based platform molecules are systematically summarized and discussed this review.

Language: Английский

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Silica-supported Fe/Fe–O nanoparticles for the catalytic hydrogenation of nitriles to amines in the presence of aluminium additives

Nature Catalysis, Journal Year: 2021, Volume and Issue: 5(1), P. 20 - 29

Published: Dec. 30, 2021

Abstract The hydrogenation of nitriles to amines represents an important and frequently used industrial process due the broad applicability resulting products in chemistry life sciences. Despite existing portfolio catalysts reported for nitriles, development iron-based heterogeneous this is still a challenge. Here, we show that impregnation pyrolysis iron(II) acetate on commercial silica produces reusable Fe/Fe–O@SiO 2 catalyst with well-defined structure comprising fayalite phase at Si–Fe interface α-Fe nanoparticles, covered by ultrathin amorphous iron(III) oxide layer, growing from matrix. These Fe/Fe–O core–shell presence catalytic amounts aluminium additives, promote all kinds including structurally challenging functionally diverse aromatic, heterocyclic, aliphatic fatty produce primary under scalable industrially viable conditions.

Language: Английский

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Toward effective electrocatalytic C–N coupling for the synthesis of organic nitrogenous compounds using CO₂ and biomass as carbon sources

SusMat, Journal Year: 2023, Volume and Issue: 3(6), P. 781 - 820

Published: Dec. 1, 2023

Abstract Thermochemical conversion of fossil resources into fuels, chemicals, and materials has rapidly increased atmospheric CO 2 levels, hindering global efforts toward achieving carbon neutrality. With the increasing push for sustainability, utilizing electrochemical technology to transform or biomass value‐added chemicals close cycle with sustainable energy sources represents a promising strategy. Expanding scope electrosynthesis is prerequisite electrification chemical manufacturing. To this end, constructing C─N bond considered priority. However, systematic review electrocatalytic processes building bonds using as not available. Accordingly, highlights research progress in organic nitrogen compounds from by coupling reactions view catalytic materials, focusing on enlightenment traditional catalysis understanding basis coupling. The possibility electrocatalysis also examined standpoints activation substrates, site, mechanism, inhibition hydrogen evolution reaction (HER). Finally, challenges prospects improved efficiency selectivity future development are 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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