Tunable mono- and di-methylation of amines with methanol over bimetallic CuCo nanoparticle catalysts

Li, Keming; Zhang, Qi; Xu, Zhong-Ming; Chen, Ran; Liu, Tiantian; Luo, Jinyue; Wu, Yang‐wen; Huang, Yao‐Bing; Lü, Qiang

doi:10.1039/d2gc00827k

Cited by 11 publications

(6 citation statements)

References 48 publications

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“…The main reason for this is because a more basic catalyst has a greater potential for facilitating isomerization reactions. However, the conversion of eugenol is low when using this kind of catalyst due to the fact that in the presence of strong bases, eugenol forms phenolic salts, which impede the methylation reaction [ 33 ]. In conclusion, the catalyst is more favorable for the conversion of eugenol when it is weakly basic, which means that it provides a favorable environment for O -methylation.…”

Section: Resultsmentioning

confidence: 99%

One-Step Green Synthesis of Isoeugenol Methyl Ether from Eugenol by Dimethyl Carbonate and Phase-Transfer Catalysts

Zhang,

Gong,

Xue

et al. 2024

Molecules

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In this paper, the green synthesis of isoeugenol methyl ether (IEME) from eugenol by O-methylation and isomerization is completed using a one-step green process. In the methylation reaction, dimethyl carbonate (DMC) was used as a green chemistry reagent instead of the traditional harmful methylation reagents, in accordance with the current concept of green chemistry. The phase transfer catalyst (PTC) polyethylene glycol 800 (PEG-800) was introduced into the isomerization reaction to break the barrier of difficult contact between solid and liquid phases and drastically reduce the reaction conditions by shortening the reaction time and reducing the alkalinity of the reaction system. The catalytic systems for the one-step green synthesis of IEME were screened, and it was shown that the catalytic system “K2CO3 + PEG-800” was the most effective. The effects of reaction temperature, n(DMC):n(eugenol) ratio, n(PEG-800):n(eugenol) ratio, and n(K2CO3):n(eugenol) ratio on eugenol conversion, IEME yield, and IEME selectivity were investigated. The results showed that the best reaction was achieved at a reaction temperature of 140 °C, a reaction time of 3 h, a DMC drip rate of 0.09 mL/min, and n(eugenol):n(DMC):n(K2CO3):n(PEG-800) = 1:3:0.09:0.08. As a result of the conversion of 93.1% of eugenol to IEME, a yield of 86.1% IEME as well as 91.6% IEME selectivity were obtained.

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Section: Resultsmentioning

confidence: 99%

One-Step Green Synthesis of Isoeugenol Methyl Ether from Eugenol by Dimethyl Carbonate and Phase-Transfer Catalysts

Zhang,

Gong,

Xue

et al. 2024

Molecules

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“…In recent years, there has been a growing interest in the use of MeOH/EtOH in N -methylation reactions. These solvents have garnered significant attention because they can serve multiple roles in one-pot reactions, acting as both hydrogen donors and methylating agents and solvents. ,, Li et al synthesized a bimetallic Cu–Co NP with suitable supports (Cu–Co/Al 2 O 3 and Cu–Co/Mg-Al-LDO) for N -methylation reaction of aniline, using methanol as the hydrogen and methylation source. Support materials also play a crucial role in enhancing the catalytic activity as the reaction conversion rate and product yield varies significantly with the support material.…”

Section: Various Hydrogen Sources For Cth Reactionsmentioning

confidence: 99%

“…(a) Plausible reaction mechanism using bimetallic CuCo catalyst for N -methylation reaction of aniline in methanol, (b) conversion plot of N -methylaniline and N -dimethylaniline against time using two different catalyst 10Cu-5Co/Al 2 O 3 and 10Cu-5Co/MgAl-LDO, (c) model reaction (MR) was studied for the poisoning of acid/base sites, (d) adsorption plot for Ph-Nh 2 , Ph-NHMe, Ph-NMe 2 using CuCo catalysts in methanol. [Reproduced with permission from ref . Copyright 2022, Royal Society of Chemistry, London.…”

Section: Various Hydrogen Sources For Cth Reactionsmentioning

confidence: 99%

Nanoarchitectonics of Non-Noble-Metal-Based Heterogeneous Catalysts for Transfer Hydrogenation Reactions: Detailed Insights on Different Hydrogen Sources

Sharma,

Choudhary,

Mittal

et al. 2024

ACS Catal.

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Catalytic transfer hydrogenation (CTH) methodology has drawn profound attention of researchers as an economical and environmentally benign alternate to conventional hydrogenation method. Unlike conventional method, CTH exhibits better reaction efficiency and atom economy, and it makes use of simple, easily accessible, low-cost hydrogen sources. Current research on CTH reactions is oriented toward the development of non-noble-metal-based catalysts due to their high abundance and potential large-scale applicability. In this Review, different organic transformation reactions, such as hydrogenation of nitroarenes, nitriles, alkenes, alkynes, and carbonyl compounds, hydrogenolysis, reductive amination, and reductive formylation reaction using different hydrogen sources have been summarized comprehensively. In addition, synthesis strategies of the non-noble-metal-based heterogeneous catalysts and the structure−activity relationship involving metal−support interaction, single-atom catalysis, and synergistic effect are highlighted. Furthermore, the optimization of the reaction parameters�such as temperature, time, solvents, and additives�for enhancing the catalytic activity and selectivity of the product are discussed in detail. This Review provides detailed insights into the recent progress made in CTH reactions using non-noble-metal-based heterogeneous catalysts with a specific focus on catalyst development, hydrogen sources, and mechanistic exploration.

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“…[3] This strategy provides straightforward synthetic methods for the construction of functional secondary and tertiary amines from simple raw materials. The reductive alkylation of nitro compounds can be regarded as a cascade reaction in one pot, where nitro compounds are firstly reduced to amines and then reductively alkylated with related alkylating reagents such as carbonyls, [4] methanol, [5] and carbon dioxide etc. [6] Specifically, recent researches focus on the reductive alkylation of nitroarenes with carbonyls [7] mainly under homogeneous and heterogeneous catalysis with transition metals such as palladium, [8] gold, [9] cobalt, [5,10] molybdenum, [11] and nickel etc [12] (Figure 1a).…”

Section: Introductionmentioning

confidence: 99%

Photoredox/Bismuth Relay Catalysis Enabling Reductive Alkylation of Nitroarenes with Aldehydes

Li,

Chen,

Xie

et al. 2024

Chemistry A European J

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The effective transition metal‐free photoredox/bismuth dual catalytic reductive dialkylation of nitroarenes with benzaldehydes has been reported. The nitroarene redution through visible light‐driven photoredox catalysis was integrated with subsequent reductive dialkylation of anilines under bismuth catalysis to enable the cascade reductive alkylation of nitroarenes with carbonyls. Salient features of this relay catalysis system include mild reaction conditions, no requirement for transition metal catalysts, easy handling, step‐economy, and high selectivity.

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Tunable mono- and di-methylation of amines with methanol over bimetallic CuCo nanoparticle catalysts

Abstract: Methylation of amines is increasingly employed as a powerful structure modification tool in medicinal chemistry, however, selectively accessing the mono- or di- methylated amines with integrated catalytic system remains a...

Cited by 11 publications

References 48 publications

One-Step Green Synthesis of Isoeugenol Methyl Ether from Eugenol by Dimethyl Carbonate and Phase-Transfer Catalysts

One-Step Green Synthesis of Isoeugenol Methyl Ether from Eugenol by Dimethyl Carbonate and Phase-Transfer Catalysts

Nanoarchitectonics of Non-Noble-Metal-Based Heterogeneous Catalysts for Transfer Hydrogenation Reactions: Detailed Insights on Different Hydrogen Sources

Photoredox/Bismuth Relay Catalysis Enabling Reductive Alkylation of Nitroarenes with Aldehydes

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