Water-soluble and reusable Ru-NHC catalyst for aqueous-phase transfer hydrogenation of quinolines with formic acid

Dalton Transactions, Journal Year: 2022, Volume and Issue: 51(21), P. 8258 - 8265

Published: Jan. 1, 2022

Water-soluble Ru-NHC complexes were synthesized and their catalytic activity was tested in the transfer hydrogenation of quinoline-type N-heteroarenes using a formic acid/sodium formate buffer solution. The unique multifunctional features designed ligand within catalyst backbone endowed it with excellent durability, reusability compatibility simple aqueous-phase operation. Thus, possible to reuse as little 0.25 mol% for three consecutive runs provide an overall turnover number around 900. A mechanistic investigation suggested that hydride generation rate-limiting step, whereas relatively facile. Furthermore, computational studies supported reaction pathway dominated by 1,4-hydride insertion at N-heteroarene substrates.

Language: Английский

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Hydrogenation and dehydrogenation of N-heterocycles under Cp*Co(iii)-catalysis

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(41), P. 14752 - 14756

Published: Jan. 1, 2023

To realize the goal of a carbon-free energy economy, it is crucial to discover reactions that utilize sustainable resources as alternatives fossil feedstocks. In this study, well-defined, air-stable Cp*Co(III)-catalyst for transfer hydrogenation quinoline derivatives and oxidative dehydrogenation cyclic amines in water developed. While former reaction promoted by formic acid reagent, latter mediated molecular oxygen sole oxidant. These processes provide new avenues investigation cobalt catalysts environmentally benign reactions.

Language: Английский

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Ir-Catalyzed Selective Reductive N-Formylation and Transfer Hydrogenation of N-Heteroarenes

Organometallics, Journal Year: 2024, Volume and Issue: 43(18), P. 2097 - 2103

Published: Sept. 3, 2024

Selective functionalization has numerous potential applications in the modification of bioactive compounds and pharmaceuticals. Herein, we advance a new approach for selective reductive N-formylation N-heteroarenes transfer hydrogenation using IrIII complexes as catalysts. The combination solvent, equivalent formic acid (FA), reaction temperature, iridium catalyst exerts high product selectivity, delivering divergent formations products excellent yields. In this process, FA can be employed not only hydrogen source but also reagent under different conditions.

Language: Английский

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A detailed DFT theoretical investigation of the mechanism of quinoline hydrogenation catalyzed by a (1,5-cyclooctadiene)rhodium(I) complex

Catalysis Today, Journal Year: 2024, Volume and Issue: unknown, P. 115160 - 115160

Published: Dec. 1, 2024

Language: Английский

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Asymmetric transfer hydrogenation of quinoline derivatives catalyzed by chiral iridium-imidazoline complex in water

Molecular Catalysis, Journal Year: 2022, Volume and Issue: 532, P. 112715 - 112715

Published: Oct. 1, 2022

Language: Английский

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Reusable water‐soluble homogeneous catalyst in aqueous‐phase transfer hydrogenation of N‐heteroarenes with formic acid: Uracil‐based bifunctional Ir‐NHC catalyst is the key

Applied Organometallic Chemistry, Journal Year: 2022, Volume and Issue: 38(10)

Published: May 4, 2022

Abstract Transfer hydrogenation of N‐heteroarenes was successfully achieved using a water‐soluble half‐sandwich Cp*Ir‐based catalyst containing uracil‐based bifunctional abnormal NHC ligand, HCOOH/HCOONa buffer solution as the hydrogen source. Reduction shown to be highly pH‐dependent, and an acidic pH = 3.0 found suitable for best activity. The showed excellent functional group compatibility high turnover number (up 10,400), with loadings low 0.005 mol%. Finally, we demonstrated catalyst's efficacy applicability toward reusable repetitive transfer liquid/liquid extraction methodology, which underscored significance sustainable usage noble metal catalysts in such transformations.

Language: Английский

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A Detailed Dft Theoretical Investigation of the Mechanism of Quinoline Hydrogenation Catalyzed by a (1,5-Cyclooctadiene)Rhodium(I) Complex

Published: Jan. 1, 2024

A detailed catalytic cycle for the hydrogenation of quinoline (Q) to 1,2,3,4-tetrahydroquinoline (THQ) catalyzed by a cationic rhodium complex containing 1,5-cyclooctadiene (COD) ligand was computationally investigated using DFT. It found that catalytically active species [Rh(COD)(kN-Q)]+ and addition each two dihydrogen molecules occurs through initial coordination forming h2-H2 intermediates, followed subsequent hydride transfer Q DHQ ligands (migratory insertion reductive elimination, respectively). Except elimination THQ product, all elementary steps were reversible, which is an important point in connection with hydrogen storage models. Our theoretical DFT calculations are consistent experimental results previously reported.

Language: Английский

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Asymmetric Transfer Hydrogenation of Stable NH Imines for the Synthesis of Enantiopure α‐Chiral Primary Amines

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(18), P. 2211 - 2216

Published: May 14, 2024

Comprehensive Summary Although it offers a direct route to access synthetically valuable α‐chiral primary amines, asymmetric transfer hydrogenation of NH imines has been rarely studied, due in large part the inaccessibility and instability imines. Herein, we report Rh‐catalyzed kind novel stable which are prepared via condensation easily available sulfonylated 2’‐aminoacetophenones with 3 methanol. With this method, enantioenriched chiral 2‐(1‐aminoalkyl)anilines, privileged pharmacore groups, have synthesized good functional group compatibility, up 99% ee. A gram‐scale reaction using 0.2 mol% catalyst successfully performed highlight practicality. Furthermore, products can be derivatized into enantiopure bioactive molecules as well tridentate ligands for metal catalysis.

Language: Английский

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Non-classical effective methods for reduction of heteroaromatic compounds

Russian Chemical Reviews, Journal Year: 2024, Volume and Issue: 93(11), P. RCR5149 - RCR5149

Published: Oct. 30, 2024

The review summarizes the known data on various methods for saturation and dearomatization of heterocyclic moieties, forming diverse aromatic compounds. Since classical hydrogenation substrates with molecular hydrogen has a number fundamental drawbacks that hinder both its use at laboratory level widespread implementation in industrial production, main attention is paid to non-classical described literature over last 20–25years. ammonia-free Birch reduction, transfer hydrogenation, reduction by Hantzsch esters some other reactions involving compounds are summarized systematized. It shown such or heterocycles can cases be more efficient than procedures.<br> bibliography includes 173 references.

Language: Английский

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Six-membered ring systems: pyridines and benzo derivatives

Progress in heterocyclic chemistry, Journal Year: 2023, Volume and Issue: unknown, P. 387 - 424

Published: Jan. 1, 2023

Language: Английский

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