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

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(22), P. 15013 - 15053

Published: Nov. 6, 2023

Methanol is a fundamental feedstock and widely used in the chemical petroleum industries. It can serve as C1 source to make variety of C–C C–N bond formation dehydrogenative coupling products, which have important applications natural products drug discovery. A high hydrogen content (12.5 wt%) methanol makes it an effective H2 donor for transfer hydrogenation various reducible functional groups. plethora transition metal-based processes been developed using methanol. Notably, recent review articles focused on aspect However, more updated that examines challenges both C1-source H2-source organic transformations contributing concept economy has not presented yet. This Review summarizes (homogeneous, heterogeneous, photo-) catalyst system C-, N-, O-methylation ketones, alcohols, amides, nitriles, heterocyclic compounds, sulfones, amines, sulfonamides direct N-methylation nitro compounds under borrowing strategy N-formylation amines acceptorless dehydrogenation source. also covers insights into reaction mechanisms role carefully selected ligands metal catalysis activation incorporation -CD3, methylation molecules. Moreover, describes groups such aldehydes, alkynes, with detail.

Language: Английский

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Efficient Cu-ZnO/TiO₂ Catalyst for Direct N-Methylation of N-Methylaniline with CO₂ and H₂

ACS Sustainable Chemistry & Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

The preparation of methyl-substituted amines by direct N-methylation with CO2/H2 is an important reaction for CO2 utilization and organic synthesis. However, the design construction effective stable non-noble-metal catalysts this remain challenging. Here, a cheap non-noble-Cu-based catalyst was prepared applied in N-methylaniline H2. 5%Cu-ZnO(3.75%)/TiO2 showed 98.8% yield initial TOF 7.7 h–1 after 24 h under 453 K, 1.5 MPa CO2, 4.5 H2, which superior to 5%Cu/TiO2, 5%Cu/ZnO, reported Cu-based catalysts. Furthermore, can be reused at least four times various excellent selectivity. characterizations experimental results that Cu0 active site, exhibited largest surface amount, thereby contributing catalytic performance. mechanism H2 proposed based on spectroscopic studies, kinetic control experiments. proceeded HCHO N-methylformanilide intermediates, formation from rate-determining step.

Language: Английский

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Recent advances of Cp*Ir complexes for transfer hydrogenation: focus on formic acid/formate as hydrogen donors

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(37), P. 7484 - 7497

Published: Jan. 1, 2023

This review summarise the transfer hydrogenation of C=O, C=C, C=N bonds unsaturated substrates via Cp*Ir complexes as catalysts and formic acid/formate hydrogen sources.

Language: Английский

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Direct use of methanol instead of formaldehyde or paraformaldehyde: Acceptorless dehydrogenative coupling for the synthesis of arylhydrazones catalyzed by a metal–ligand iridium bifunctional catalyst

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 438, P. 115685 - 115685

Published: Aug. 3, 2024

Language: Английский

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Efficient N-Methylation of Primary Amides Using Methanol Under Mn(I)-Catalysis

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134535 - 134535

Published: Feb. 1, 2025

Language: Английский

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Heterogeneous Cobalt Nanocatalyst for Reductive Transformation of Nitroarenes to Aryl Amines Using Isopropanol as a Hydrogen Source

Industrial & Engineering Chemistry Research, Journal Year: 2025, Volume and Issue: unknown

Published: March 19, 2025

Herein, we introduce an efficient catalytic transfer hydrogenation method using inexpensive, environmentally friendly, and readily available isopropyl alcohol as a hydrogen donor for selectively reducing diverse nitroarenes. The process employs cobalt-based nanocatalyst (Co–N/Al2O3), synthesized via simple impregnation cobalt nitrate, 1,10-phenanthroline, γ-Al2O3 precursors. This proves highly effective in producing wide range of aryl amines (35 examples), pharmaceutical intermediates (4 late-stage functional group transformations (1 example), with yields ranging from moderate to excellent (70–98%) across various scales. catalyst was characterized HR-TEM, powder XRD, XPS, H2-TPR, N2 adsorption–desorption, Raman spectroscopy, ICP-OES techniques. These analyses confirmed the formation Co3O4 nanoparticles. exceptional performance Co–N/Al2O3 is attributed its optimized textural, morphological, acidic properties, which are superior other catalysts. Mechanistic studies provided insights into formed during different stages reaction indirect route (condensation mechanism). recyclability were validated through experimental testing, demonstrating consistent efficiency over three consecutive cycles. sustainable offers promising alternative conventional processes that use molecular hydrogen.

Language: Английский

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Formic acid dehydrogenation using Ruthenium-POP pincer complexes in ionic liquids

Scientific Reports, Journal Year: 2024, Volume and Issue: 14(1)

Published: Oct. 31, 2024

Formic acid is one of the most promising candidates for long-term storage hydrogen in liquid form. Herein, we present a new collection ruthenium pincer complexes general formula [RuHCl(POP)(PPh3)] using commercially available or easy-to-synthesize tridentate xantphos-type POP ligands. We applied these dehydrogenation formic to CO2 and H2 ionic BMIM OAc (1-butyl-3-methylimidazolium acetate) as solvent under mild, reflux-free conditions. The best performing catalyst with respect maximum turnover frequency, literature-known complex [RuHCl(xantphos)(PPh3)] Ru-1, produced frequency 4525 h−1 74% conversion after 10 min at 90 °C complete (> 98%) occurring within 3 h. On other hand, overall catalyst, novel [RuHCl(iPr-dbfphos)(PPh3)] Ru-2, facilitated full 1 h leading an 1009 h−1. Moreover, catalytic activity was observed temperatures low 60 °C. Only are gas phase, no CO detected. High-resolution mass spectrometry suggests presence N-heterocyclic carbene reaction mixture.

Language: Английский

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Synthesis of Ru‐PNPC Pincer Complexes and Applications in Catalytic Hydrogenation and Dehydrogenation Reactions

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 28, 2024

Abstract The reaction of N , ‐bis(2‐(diisopropylphosphaneyl)ethyl)prop‐2‐yn‐1‐amine 1 with [Ru(CO)ClH(PPh 3 ) ] leads to the formation a new class cyclometallated PNPC pincer complexes. Several examples this compounds are synthesized and characterized. They, specifically complexes 2 show good excellent activity selectivity in additive‐free formic acid dehydrogenation, transfer (de)hydrogenation reactions different functional groups (ketone, alkyne, alcohol). Theoretical experimental studies reveal two competing pathways for dehydrogenation acid. Ru‐H pathway proceeds via coordination site trans propylene arm ligand, whereas Ru‐C pathway, de‐coordination is observed.

Language: Английский

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Catalytic Amination of Alcohols Using Diazo Compounds under Manganese Catalysis Through Hydrogenative N‐Alkylation Reaction

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(61)

Published: July 24, 2023

Abstract Sustainable chemical production requires fundamentally new types of catalysts and catalytic technologies. The development coherent robust systems based on earth‐abundant transition metals is essential, but highly challenging. Herein, we systematically explored a general hydrogenative cleavage/N‐alkylation tandem cyclic acyclic diazo (N=N) compounds to value‐added amines under manganese catalysis. reaction catalyzed by single‐site molecular complex proceeds via dehydrogenation, transfer hydrogenation, borrowing hydrogenation strategies. Interestingly, the involves abundantly available renewable feedstocks, such as alcohols, that can act (transfer)hydrogenating alkylating agents. synthetic application our approach in large‐scale pharmaceutical synthesis easy access demanding N ‐CH 3 /CD derivatives are also demonstrated. Kinetic studies show rate depends concentration alcohol Mn‐catalyst follows fractional orders. Several selective bond activation/formation reactions occur sequentially amine–amide metal‐ligand cooperation.

Language: Английский

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Hydrogen transfer reaction to imines with 2-propanol catalyzed by ruthenium (II) complexes containing nitrogen-phosphorus (NPN) ligands. Experimental and computational studies

Inorganica Chimica Acta, Journal Year: 2024, Volume and Issue: 568, P. 122064 - 122064

Published: April 16, 2024

Language: Английский

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