Reductive Coupling of Nitroarenes and HCHO for General Synthesis of Functional Ethane-1,2-diamines by a Cobalt Single-Atom Catalyst

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(31), P. 17329 - 17336

Published: July 7, 2023

Despite the extensive applications, selective and diverse access to N,N'-diarylethane-1,2-diamines remains, date, a challenge. Here, by developing bifunctional cobalt single-atom catalyst (CoSA-N/NC), we present general method for direct synthesis of such compounds via reductive coupling cheap abundant nitroarenes formaldehyde, featuring good substrate functionality compatibility, an easily accessible base metal with excellent reusability, high step atom efficiency. Mechanistic studies reveal that N-anchored single atoms (CoN4) serve as catalytically active sites reduction processes, N-doped carbon support enriches HCHO timely trap in situ formed hydroxyamines affords requisite nitrones under weak alkaline conditions, subsequent inverse electron demand 1,3-dipolar cycloaddition imines followed hydrodeoxygenation cycloadducts furnishes products. In this work, concept catalyst-controlled nitroarene create specific building blocks is anticipated develop more useful chemical transformations.

Language: Английский

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Heterogeneous Iridium-Catalyzed Carbene N–H Bond Insertion with α-Alkyl Diazo Esters

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4690 - 4698

Published: March 13, 2024

A heterogeneous iridium single-atom site catalyst (Ir-SA) was synthesized and investigated in catalyzing the carbene insertion reaction with challenging α-alkyl diazo ester substrates. With only 0.23 mol % loading, our Ir-SA demonstrated remarkable performance N–H bond reactions involving various (hetero) aryl amines coupled esters. Notably, case of using a chiral diamino substrate two reactive sites, exhibited high selectivity toward single insertion, leading to generation class unsymmetric ligands. Further mechanism study revealed that lower activation barrier associated step, as compared either β-hydride elimination or downstream dual accounted for observed this catalyzed by Ir-SA.

Language: Английский

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Reduction-Interrupted Tandem Reaction for General Synthesis of Functional Amino Acids by a Heterogeneous Cobalt Catalyst

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 11, 2025

Despite their significant importance in numerous fields, the challenges direct and diverse synthesis of γ-amino-α-hydroxybutyric acids (AHBAs) pose substantial obstacles to explore functions. Here, by preparation a N-doped carbon-supported bifunctional cobalt catalyst (Co-DAPhen/C), it was applied develop reductive tandem reaction for general AHBA derivatives from cheap abundant nitroarenes, formaldehyde, acrylates. This catalytic three-component features broad substrate functionality tolerance, an easily accessible reusable catalyst, high step atom economy. The active Co sites are involved mild reduction processes with formic acid, whereas carbon support enriches HCHO acrylates physical adsorption, thus favoring capture hydroxylamine nitrone intermediates via condensation 1,3-dipolar cycloaddition, respectively. Such metal–support synergy interrupts conventional nitroarenes into anilines results novel route. In this work, concept merging effective intermediate transformations is anticipated more useful reactions rational design.

Language: Английский

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A general and robust Ni-based nanocatalyst for selective hydrogenation reactions at low temperature and pressure

Science Advances, Journal Year: 2023, Volume and Issue: 9(48)

Published: Dec. 1, 2023

Catalytic hydrogenations are important and widely applied processes for the reduction of organic compounds both in academic laboratories industry. To perform these reactions sustainable practical manner, development applicability non-noble metal–based heterogeneous catalysts is crucial. Here, we report highly active air-stable nickel nanoparticles supported on mesoporous silica (MCM-41) as a general selective hydrogenation catalyst. This catalytic system allows carbonyl compounds, nitroarenes, N-heterocycles, unsaturated carbon─carbon bonds good to excellent selectivity under very mild conditions (room temperature 80°C, 2 10 bar H ). Furthermore, optimal nickel/meso–silicon dioxide catalyst reusable (4 cycles) without loss its activity.

Language: Английский

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Construction of Indium(III)–Organic Framework Based on a Flexible Cyclotriphosphazene-Derived Hexacarboxylate as a Reusable Green Catalyst for the Synthesis of Bioactive Aza-Heterocycles

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(12), P. 5446 - 5463

Published: March 8, 2024

The constant demand for eco-friendly methods of synthesizing complex organic compounds inspired researchers to design and develop modern, highly efficient heterogeneous catalytic systems. Herein, In-HCPCP metal–organic framework (SRMIST–1), a Lewis acid catalyst containing less toxic indium robust cyclotriphosphazene exhibiting notable chemical thermal stability, durable activity, exceptional reusability was produced through the reaction between indium(III) nitrate hydrate hexakis(4-carboxylatophenoxy)-cyclotriphosphazene. In SRMIST–1 structure, secondary building units {InO7} are assembled by connection η2- η1-carboxylic oxo atoms from different HCPCP ligands, forming three-dimensional network. occurrence regularly distributed In(III) sites in confers superior reactivity on toward synthesis 2,3-dihydroquinazolin-4(1H)-ones 3,4-dihydro-2H-1,2,4-benzothiadiazine-1,1-dioxides cyclization 2-aminobenzamides 2-aminobenzenesulphonamides with aldehydes under optimized conditions, respectively. features this method include broad functional group compatibility, low loading (1–5 mol %), mild easy workup procedures, good excellent yields, ethanol as green solvent, (five cycles), economic attractiveness, which is mainly due sustainability reusable catalyst. Our findings demonstrate that reactive finds widespread applications medicinal chemistry.

Language: Английский

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Promotion Effect of Pd in the Ru/C-Catalyzed Hydrogenation of Benzofurans

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2719 - 2729

Published: Feb. 7, 2024

The selective hydrogenation of benzofurans (BFs) over supported metal catalysts is fundamental interest for producing biologically active and pharmacologically relevant chemicals. However, most are confronted with the dilemmas activity selectivity. Herein, we report that deposition a small amount Pd on commercial Ru/C makes inactive in BF at low temperatures (e.g., 4 °C), selectivity to 2,3-dihydrobenzofuran as high 92% was obtained. Systematic investigations show catalytic performance Pd^Ru/C attributed synergy Ru, respectively, activation H2 significantly reduced energy barrier C1 (O–C1═C2) addition step due interaction between oxyphilic Ru. Besides, series bioactive compounds could be successfully produced by derivatives catalyst. This study provides insights into O-containing heteroaromatics incorporation sites catalysts.

Language: Английский

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Multi-hydroxyl POSS supported iridium complexes as a recyclable catalyst for selective synthesis of N-/C-substituted indoles and the total synthesis of HIV-1 fusion inhibitor

Journal of Catalysis, Journal Year: 2023, Volume and Issue: 429, P. 115205 - 115205

Published: Nov. 24, 2023

Language: Английский

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Dearomative selective reduction of structurally diverse N-heteroarenes enabled by a homogeneous titanium catalyst

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 115937 - 115937

Published: Jan. 1, 2025

Language: Английский

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Improving the Hydrogenation Performance of Nano‐Catalysts by Constructing a Cavity‐Constrained Fluidized System

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 21, 2025

Nano-catalysts demonstrate exceptional performance in heterogeneous reactions, yet their potential is often underutilized due to a lack of attention engineering design. In this study, an innovative encapsulated structure presented for nano-catalysts and corresponding catalytic system. Using oil-in-water droplet strategy, millimeter-sized hollow spherical alumina (Al2O3-HS) fabricated with average diameter ≈3 mm void size ≈1 mm. This approach enables the one-step encapsulation nanoscale Pd/Al2O3 within Al2O3-HS. The resulting assembly immobilized tubular reactor hydrogenation 2-ethylanthraquinone, hydrogen introduced from bottom reactor. Remarkably, catalyst achieved twice H2O2 productivity conventional supported catalysts. enhancement attributed cavity-constrained fluidization behavior spheres. design introduces novel system that combines shell-immobilization nano-catalysts. As gas velocity exceeds minimum velocity, particles remain highly accessible while allowing efficient product flow. hybrid integrates advantages fixed-bed fluidized-bed systems, offering promising solution technical challenges limiting industrial application

Language: Английский

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Recent Advances in the 3 d‐Transition‐Metal‐Catalyzed Synthesis of Isoquinolines and its Derivatives

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(24), P. 4458 - 4494

Published: Nov. 24, 2023

Abstract The preservation of scarce rare earth metals, such as palladium, rhodium, iridium, and others, poses a significant challenge for humanity due to their limited availability. These metals might be replaced by earth‐abundant 3d‐transition cobalt, manganese, iron, nickel, copper, etc . Isoquinolines have acquired an important position in synthetic organic chemistry well medicinal chemistry. They manifest diverse range natural molecules, serving pivotal synthons the synthesis numerous bioactive compounds with notable significance. Numerous reports on isoquinoline derivatives via transition metal catalysis been published worldwide. In this review, we summarize recent approaches synthesizing various using 3d‐transition‐metal catalysts since 2020. review has divided into different 3d‐transition‐metal‐based catalysis. We expect that will bring better overview present status progress made isoquinolines persuade more advancements research area near future.

Language: Английский

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