Highly Active and Sulfur-Tolerant Ruthenium Phosphide Catalyst for Efficient Reductive Amination of Carbonyl Compounds

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4501 - 4509

Published: March 12, 2024

The catalysis of precious metal phosphides in liquid-phase molecular transformations has rarely been explored. Herein, we reveal the remarkable performance ruthenium phosphide nanoparticles supported on activated carbon (Ru2P/C) as a highly efficient heterogeneous catalyst for reductive amination carbonyl compounds. Typically, Ru2P/C exhibited high activity even under 1 bar H2/NH3 mixed gas, sharp contrast to conventional Ru catalysts that require H2 pressure (H2 2.5–40 bar). Furthermore, demonstrated versatility across aliphatic, aromatic, and heteroaromatic compounds, providing corresponding amines yields. Notably, tolerance toward sulfur-containing known their potential strongly coordinate with active species, leading deactivation. Comprehensive studies based control experiments, kinetic studies, spectroscopic analyses, temperature-programmed desorption measurements, evaluations H2–D2 exchange rates revealed multiple properties significantly contribute its catalytic efficiency. These encompassed H2-activation ability, acidic property formation imine intermediates, sulfur derived from ensemble effect Ru–P bond formation.

Language: Английский

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Homogeneous cobalt-catalyzed reductive amination for synthesis of functionalized primary amines

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

Published: Nov. 29, 2019

Abstract The development of earth abundant 3d metal-based catalysts continues to be an important goal chemical research. In particular, the design base metal complexes for reductive amination produce primary amines remains as challenging. Here, we report combination cobalt and linear-triphos (bis(2-diphenylphosphinoethyl)phenylphosphine) molecularly-defined non-noble catalyst synthesis linear branched benzylic, heterocyclic aliphatic from carbonyl compounds, gaseous ammonia hydrogen in good excellent yields. Noteworthy, this exhibits high selectivity a result -NH 2 moiety is introduced functionalized structurally diverse molecules. An inner-sphere mechanism on basis mono-cationic [triphos-CoH] + complex active proposed supported with density functional theory computation doublet state potential free energy surface H metathesis found rate-determining step.

Language: Английский

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Nickel-Catalyzed Direct Synthesis of Quinoxalines from 2-Nitroanilines and Vicinal Diols: Identifying Nature of the Active Catalyst

The Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 85(4), P. 2775 - 2784

Published: Jan. 6, 2020

The inexpensive and simple NiBr2/1,10-phenanthroline system-catalyzed synthesis of a series quinoxalines from both 2-nitroanilines 1,2-diamines is demonstrated. reusability test for this system was performed up to the seventh cycle, which afforded good yields desired product without losing its reactivity significantly. Notably, during catalytic reaction, formation heterogeneous Ni-particle observed, characterized by PXRD, XPS, TEM techniques.

Language: Английский

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

ChemSusChem, Journal Year: 2020, Volume and Issue: 13(12), P. 3110 - 3114

Published: April 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.

Language: Английский

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Efficient and Mild Reductive Amination of Carbonyl Compounds Catalyzed by Dual-Function Palladium Nanoparticles

ACS Sustainable Chemistry & Engineering, Journal Year: 2019, Volume and Issue: 8(3), P. 1618 - 1626

Published: Dec. 31, 2019

Primary amines are valuable building blocks for a large number of chemicals, developing efficient synthetic routes toward primary and particularly those proceeding under mild conditions highly desirable rather challenging. Presented here is procedure enabling itself to proceed in H2O using H2 1 atm (0.1 MPa) the reductive amination carbonyl compounds. Several palladium-based nanoparticle (Pd-NP) catalysts were prepared, one emerged be most suitable classified as nanoparticles, due its high catalytic activity, reactions allowed at room temperature NH3, corresponding can afforded with yields up 99%. Some control carried out, revealing that pivotal activating Pd-NPs. The fact Pd-NPs catalyze both compounds hydrogenation imines proves dual-function catalyst, plausible mechanism was proposed.

Language: Английский

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Recent Progress on Catalytic Addition Reactions toN-Unsubstituted Imines

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(12), P. 6924 - 6951

Published: May 27, 2020

Catalytic addition reactions to N-unsubstituted (N-unprotected) imines can provide a more straightforward synthesis of amines. This direct process eliminates the unnecessary protecting-group manipulations that are required with N-substituted (N-protected) and contribute development green chemistry. Although their use has been limited due difficulties associated nature imines, recently developed catalytic methods enable as electrophiles in various reactions. To facilitate an understanding state art synthetic methodologies, herein we review recent progress on imines. We begin overview chemistry followed by summary categorized according reaction type. hope this will help stimulate further greener syntheses nitrogen-containing compounds.

Language: Английский

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Ultra-small cobalt nanoparticles from molecularly-defined Co–salen complexes for catalytic synthesis of amines

Chemical Science, Journal Year: 2020, Volume and Issue: 11(11), P. 2973 - 2981

Published: Jan. 1, 2020

We report the synthesis of in situ generated cobalt nanoparticles from molecularly defined complexes as efficient and selective catalysts for reductive amination reactions.

Language: Английский

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

JACS Au, Journal Year: 2021, Volume and Issue: 1(4), P. 501 - 507

Published: April 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.

Language: Английский

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Nanoparticles and single atoms of cobalt synergistically enabled low-temperature reductive amination of carbonyl compounds

Chemical Science, Journal Year: 2022, Volume and Issue: 13(31), P. 9047 - 9055

Published: Jan. 1, 2022

Low-temperature and selective reductive amination of carbonyl compounds is a highly promising approach to access primary amines. However, it remains great challenge conduct this attractive route efficiently over earth-abundant metal-based catalysts. Herein, we designed several Co-based catalysts (denoted as Co@C-N(x), where x represents the pyrolysis temperature) by metal-organic framework ZIF-67 at different temperatures. Very interestingly, prepared Co@C-N(800) could catalyze various aldehydes/ketones synthesize corresponding amines with high yields 35 °C. Besides non-noble metal mild temperature, other unique advantage catalyst was that substrates reduction-sensitive groups be converted into selectively because not active for these low temperature. Systematic analysis revealed composed graphene encapsulated Co nanoparticles atomically dispersed Co-N sites. The particles promoted hydrogenation step, while sites acted acidic activate intermediate (Schiff base). synergistic effect metallic crucial excellent performance Co@C-N(800). To best our knowledge, first study on efficient synthesis via temperature (35 °C).

Language: Английский

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Efficient light-driven reductive amination of furfural to furfurylamine over ruthenium-cluster catalyst

Journal of Energy Chemistry, Journal Year: 2022, Volume and Issue: 76, P. 239 - 248

Published: Sept. 20, 2022

Language: Английский

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