Transition metals-catalyzed amination of biomass feedstocks for sustainable construction of N-heterocycles

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 502, P. 215622 - 215622

Published: Dec. 26, 2023

Language: Английский

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Carbon-based catalysts: advances in synthesizing N-heterocyclic compounds using graphene family and graphite oxide

Research on Chemical Intermediates, Journal Year: 2024, Volume and Issue: 50(2), P. 485 - 531

Published: Jan. 5, 2024

Language: Английский

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N-Alkylation of Amines by C1–C10 Aliphatic Alcohols Using A Well-Defined Ru(II)-Catalyst. A Metal–Ligand Cooperative Approach

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(9), P. 5944 - 5961

Published: April 13, 2023

A Ru(II)-catalyzed efficient and selective N-alkylation of amines by C1-C10 aliphatic alcohols is reported. The catalyst [Ru(L1a)(PPh3)Cl2] (1a) bearing a tridentate redox-active azo-aromatic pincer, 2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline (L1a) air-stable, easy to prepare, showed wide functional group tolerance requiring only 1.0 mol % (for N-methylation N-ethylation) 0.1 loading for with C3-C10 alcohols. array N-methylated, N-ethylated, N-alkylated were prepared in moderate good yields via direct coupling 1a efficiently catalyzes the diamines selectively. It even suitable synthesizing using (aliphatic) diols producing tumor-active drug molecule MSX-122 yield. excellent chemo-selectivity during oleyl alcohol monoterpenoid β-citronellol. Control experiments mechanistic investigations revealed that 1a-catalyzed reactions proceed borrowing hydrogen transfer pathway where removed from dehydrogenation step stored ligand backbone 1a, which subsequent steps transferred situ formed imine intermediate produce amines.

Language: Английский

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Zn(II)‐Stabilized Azo‐Anion Radical Catalyzed Sustainable C−C Bond Formation: Regioselective Alkylation of Fluorene, Oxindole, and Indoles

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(10)

Published: Feb. 7, 2024

Abstract Herein we report a sustainable approach for the alkylation of ketones, 9 H ‐fluorene, oxindole, and indole using alcohols as alkylating agent catalyzed by well‐defined air‐stable zinc catalyst ( 1 ) tridentate redox non‐innocent arylazo ligand, 2‐((4‐chlorophenyl)diazenyl)‐1,10‐phenanthroline L ). 2–3 mol % efficiently produces substituted α‐alkylated 9‐alkylated fluorenes, C3 ‐alkylated oxindoles, indoles in moderate to good isolated yields. In aerial condition, formation bis(indolyl)methane (BIMs) derivatives were observed when subjected primary alcohols. A few drug molecules containing BIMs prepared The exhibited chemoselectivity during functionalization fluorene with oleyl alcohol β‐citronellol. control experiments, including deuterium labeling performed unveil reaction mechanism indicate that one‐electron reduced azo‐anion radical species [ ]‐formed situ, acts active catalyst. All events occur at redox‐active aryl‐azo which reservoir hydrogen electrons throughout catalytic cycle, keeping Zn(II)‐center template.

Language: Английский

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Indazole enhances Ru-catalyzed hydrogenation of unsaturated bonds

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A practical approach is presented for the highly selective hydrogenation of various unsaturated compounds using a cutting-edge Ru/PNN catalytic system, resulting in high turnover numbers and substantial production valuable pharmaceuticals.

Language: Английский

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Synthesis, Characterization and Application of NNN Pincer Manganese Complexes with Pyrazole Framework in α-Alkylation Reaction

Molecules, Journal Year: 2025, Volume and Issue: 30(7), P. 1465 - 1465

Published: March 26, 2025

A series of novel NNN pincer manganese complexes based on pyrazole skeleton 4 were efficiently synthesized in a two-step process. All the new fully characterized by 1H, 13C NMR spectra. Furthermore, molecular structures 4a and 4c also determined X-ray single-crystal diffraction. The manganese(I) catalysts obtained showed efficient catalytic activity α-alkylation reaction ketones with alcohols. Under optimal conditions, expected products procured moderate to high yields.

Language: Английский

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NNN pincer palladium(II) complexes with N-(2-(1H-pyrazol-1-yl)phenyl)-picolinamide ligands: synthesis, characterization, and application to heck coupling reaction

Transition Metal Chemistry, Journal Year: 2024, Volume and Issue: 49(3), P. 149 - 159

Published: Jan. 28, 2024

Language: Английский

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Multicomponent synthesis via acceptorless alcohol dehydrogenation: an easy access to tri-substituted pyridines

RSC Advances, Journal Year: 2024, Volume and Issue: 14(15), P. 10761 - 10767

Published: Jan. 1, 2024

The multicomponent synthesis of 2,4,6-trisubstituted pyridine via acceptorless alcohol dehydrogenation using ammonium acetate as a nitrogen source catalyzed by hydroxyapatite-supported palladium nanoparticles heterogeneous catalyst.

Language: Английский

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Electron transfer catalysis mediated by 3d complexes of redox non-innocent ligands possessing an azo function: a perspective

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(43), P. 15627 - 15646

Published: Jan. 1, 2023

It was first reported almost two decades ago that ligands with azo functions are capable of accepting electron(s) upon coordination to produce azo-anion radical complexes, thereby exhibiting redox non-innocence. Over the past decades, there have been numerous reports such complexes along their structures and diverse characteristics. The ability a coordinated function accept one or more electron(s), acting as an electron reservoir, is currently employed carry out transfer catalysis since they can undergo transformation at mild potentials due presence energetically accessible energy levels. cooperative involvement non-innocent ligand(s) containing group metal centre adjust modulate Lewis acidity latter through selective ligand-centred events, manipulating capacity bind substrate. We summarized list row transition iron, cobalt, nickel, copper zinc incorporating exploited catalysts effectuate sustainable synthesis wide variety useful chemicals. These include ketazines, pyrimidines, benzothiazole, benzoxazoles, N-acyl hydrazones, quinazoline-4(3)H-ones, C-3 alkylated indoles, N-alkylated anilines heteroamines. reaction pathways, demonstrated by catalytic loops, reveal ligand act sink in initial steps bring about alcohol oxidation thereafter, serve pool final products either via HAT PCET processes.

Language: Английский

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Oxygen Dependent Switchable Selectivity during Ruthenium Catalyzed Selective Synthesis of C3-Alkylated Indoles and Bis(indolyl)methanes

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(24), P. 16755 - 16772

Published: Nov. 28, 2023

Herein, we report a ligand-centered redox-controlled oxygen-dependent switchable selectivity during ruthenium-catalyzed selective synthesis of C3-alkylated indoles and bis(indolyl)methanes (BIMs). A wide variety BIMs were prepared selectively in moderate to good isolated yields by coupling alcohols, catalyzed well-defined, air-stable, easy-to-prepare Ru(II)-catalyst (1a) bearing redox-active tridentate pincer (L1a). Catalyst 1a efficiently the C3-alkylation under an argon atmosphere while, oxygen environment, exclusively producing BIMs. few drug molecules containing also synthesized efficiently. exhibited excellent chemoselectivity with alcohols internal carbon–carbon double bonds. Mechanistic investigation revealed that coordinated azo-aromatic ligand actively participates catalysis. During dehydrogenation azo-moiety stores hydrogen removed from subsequently transfers alkylideneindolenine intermediate, forming indoles. While transfer scaffold molecular generates H2O2, leaving no scope for hydrogenation rather than it undergoing 1,4-Michael-type addition

Language: Английский

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