Methanol as a greener C1 synthon under non-noble transition metal-catalyzed conditions

Sheetal, .; Mehara, Pushkar; Das, Pralay

doi:10.1016/j.ccr.2022.214851

Cited by 21 publications

(8 citation statements)

References 183 publications

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“…Just in the past few years, there are some reviews focusing on this N-methylation of amines. Das et al [14] and Balaraman et al [15] have specifically reviewed on CH 3 OH-based N-methylation of amines, respectively. Liu and Ma [16] gave a specific review on CO 2 -based N-methylation of amines in 2021.…”

Section: Introductionmentioning

confidence: 99%

Catalysis‐Controlled Selective N‐mono or N‐di‐methylation of Anilines: A Review on Synthesis of N‐methyl or N,N‐dimethyl anilines

Zhang,

Chen,

Min

et al. 2024

ChemistrySelect

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N‐alkyl anilines are a series of common and versatile compounds which not only have been used as reaction solvents, acid‐accepters, and organic‐bases, but also in synthesis of dyes, pharmaceuticals, and anti‐colodal. The N‐methyl and/or N,N‐dimethyl anilines are the most representative ones among these. Due to their widespread uses, numerous works have been reported on synthetic strategies in the past decades. The studies on N−H methylations of anilines mainly focus on selection of reagents, selection of catalysts, or ligands design. Different transition‐metals, e. g., Ir, Ru, Pd, and et. al, with different ligands have been used in the methylation protocols. Methanol (CH3OH), carbon dioxide (CO2), formaldehyde (HCHO), or dimethyl carbonate ((CH3)2CO3) was used as C source, and hydrogen (H2) or silanes as H source. In this work, we would like to summarize the latest advances on the synthesis of N‐methyl (N,N‐dimethyl included) anilines and derivatives. This review provides an overview of reactants and catalyst, as well as an emphasis on the scope of substrates and proposed reaction mechanism for each work.

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Section: Introductionmentioning

confidence: 99%

Catalysis‐Controlled Selective N‐mono or N‐di‐methylation of Anilines: A Review on Synthesis of N‐methyl or N,N‐dimethyl anilines

Zhang,

Chen,

Min

et al. 2024

ChemistrySelect

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“…The utilization of simple and readily available feedstock renewables for sustainable and affordable chemical synthesis is a primary focus in contemporary science. , In this perspective, methanol, easily derivable in many ways, has manifold applications in academic and applied research for producing value-added chemicals. − ,, Methanol is a valuable C1 source and H 2 surrogate that can be a clean and ideal alternative to hazardous reagents in various applications. − Catalytic reduction of functional groups is one of the key chemical reactions in organic synthesis, and the methyl group is an essential structural component bound to C, N, or oxygen in many pharmacological drugs and bioactive substances. , Therefore, organometallic catalysis has witnessed significant development of molecularly defined complexes in the past decade, enabling revolutionary trends in organic synthesis using methanol as a C1 and potential H 2 source. − Limited review articles have documented the importance and challenges of methanol as a C1 and H 2 source via catalytic (de)hydrogenation strategies (Figure a,b). ,,− However, they only focused on recent developments for methanol as a C1 source and mostly covered precious metal-based catalysis. Thus, a comprehensive review of the application of methanol as both a C1 and an H 2 source could be of interest to researchers in academia and industry.…”

Section: Introductionmentioning

confidence: 99%

Multi-Functionality of Methanol in Sustainable Catalysis: Beyond Methanol Economy

Sivakumar,

Kumar,

Yadav

et al. 2023

ACS Catal.

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Methanol is a fundamental feedstock and is widely used in the chemical and petroleum industries. It can serve as a C1 source to make a variety of C−C and C−N bond formation and dehydrogenative coupling products, which have important applications in natural products and drug discovery. A high hydrogen content (12.5 wt%) of methanol makes it an effective H 2 donor for the transfer hydrogenation of various reducible functional groups. A plethora of various transition metal-based dehydrogenative processes have been developed using methanol. Notably, recent review articles focused on the C1 aspect of methanol. However, a more updated review that examines the challenges and applications of methanol as both a C1-source and H 2 -source in organic transformations contributing to the concept of the methanol economy has not been presented yet. This Review summarizes the transition metal-based (homogeneous, heterogeneous, and photo-) catalyst system for C-, N-, and O-methylation of ketones, alcohols, amides, nitriles, heterocyclic compounds, sulfones, amines, amides, sulfonamides and direct N-methylation of nitro compounds under borrowing hydrogen strategy and N-formylation of amines using methanol under acceptorless dehydrogenation coupling using methanol as a C1 source. It also covers insights into reaction mechanisms and the role of carefully selected ligands in the metal catalysis for methanol activation and incorporation of -CD 3 , methylation of drug molecules. Moreover, it describes transfer hydrogenation of various functional groups such as aldehydes, ketones, alkynes, and nitro with methanol as an H 2 donor in detail.

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“…Methanol is a versatile and promising component in sustainable energy and chemical sectors due to its easy handling, cost-effectiveness, and availability from renewable resources. − The acceptorless dehydrogenation of methanol to carbon monoxide and hydrogen represents an attractive strategy for nonfossil syngas formation. This reaction has been mainly achieved through heterogeneous catalysts, such as M-based (M = Cu, Ni, Pd, Pt), − bimetallic Cu-M/CeO 2 (M = Ni, Pd, Pt), Cu–Al spinel oxide, and single-site catalysts (Pt 1 /CeO 2 ). , Although heterogeneous catalysts have made significant progress in terms of stability and activity, they are mostly carried out at high temperatures above 200 °C.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insight into Acceptorless Dehydrogenation of Methanol to Syngas Catalyzed by MACHO-Type Ruthenium and Manganese Complexes: A DFT Study

Yang,

Guo,

Ren

et al. 2023

Inorg. Chem.

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The acceptorless dehydrogenation of methanol to produce carbon monoxide (CO) and dihydrogen (H2) mediated by MACHO-type 1-Ru and 1-Mn complexes was theoretically investigated via density functional theory calculations. The 1-Ru-catalyzed process involves the formation of active species 4-Ru through a methanol-bridged H2 release pathway. Methanol dehydrogenation by 4-Ru yields formaldehyde and 1-Ru, followed by H2 release to regenerate 4-Ru (rate-determining step, ΔG ‡ = 32.5 kcal/mol). Formaldehyde further reacts with methanol via nucleophilic attack of the MeO– ligand in the Ru complex (ΔG ‡ = 9.6 kcal/mol), which is more favorable than the traditional methanol-to-formaldehyde nucleophilic attack (ΔG ‡ = 33.8 kcal/mol) due to the higher nucleophilicity of MeO–. CO is ultimately produced through the methyl formate decarbonylation reaction. Accelerated H2 release in the early reaction stage compared to CO results from the initial methanol dehydrogenation and condensation of formaldehyde with methanol. In contrast, CO generation occurs later via methyl formate decarbonylation. The 1-Mn-catalyzed reaction has reduced efficiency compared to 1-Ru for the higher Gibbs energy barrier (ΔG ‡ = 34.1 kcal/mol) of the rate-determining step. Excess NaO t Bu promotes the reaction of CO and methanol, forming methyl formate, significantly reducing the CO/H2 ratio as the catalyst amount decreases. These findings deepen our understanding of the methanol-to-syngas transformation and can drive progress in this field.

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Methanol as a greener C1 synthon under non-noble transition metal-catalyzed conditions

Cited by 21 publications

References 183 publications

Catalysis‐Controlled Selective N‐mono or N‐di‐methylation of Anilines: A Review on Synthesis of N‐methyl or N,N‐dimethyl anilines

Catalysis‐Controlled Selective N‐mono or N‐di‐methylation of Anilines: A Review on Synthesis of N‐methyl or N,N‐dimethyl anilines

Multi-Functionality of Methanol in Sustainable Catalysis: Beyond Methanol Economy

Mechanistic Insight into Acceptorless Dehydrogenation of Methanol to Syngas Catalyzed by MACHO-Type Ruthenium and Manganese Complexes: A DFT Study

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