Cobalt Nanoparticles catalyzed N‐Heterocycles Synthesis via Acceptorless Dehydrogenative Coupling

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: July 29, 2024

Abstract The acceptorless dehydrogenation reaction is a sustainable and atom‐economical methodology in organic synthesis, resulting the byproducts of only hydrogen or water. Herein, robust Co−Si/CN catalyst (derived from ZIF@SiO 2 composite) has been synthesized through one‐step assembly process via pyrolysis etching. This employed for dehydrogenative coupling 2‐aminoalcohols with secondary alcohols, enabling efficient conversion various substrates into desired quinoline pyridine derivatives yield up to 94 %.

Language: Английский

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Shaking Up the Friedländer Reaction: Rapid, Scalable Mechanochemical Synthesis of Polyaryl‐substituted Quinolines

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 16, 2024

Abstract Quinolines are ubiquitous heterocyclic aromatic scaffolds, which can be found in many natural and synthetic products. They highly valued for their pharmacological electrochemical properties, encouraging the discovery of new routes quinoline synthesis diversification. In particular, polyaryl‐substituted quinolines have recently surged as useful substrates a wide variety applications, yet remain difficult inefficient. Herein, we report rapid novel mechanochemical Friedländer under basic conditions using ball milling. The optimized reaction resulted moderate to excellent yields ranging from 48% >95% demonstrated broad functional group tolerance at 1 hour times. We further show route photocatalyst DPQN 2,4−di−OMe photo‐ligand PPQN well OLED donor‐acceptor pCzPPQ, electron transport material oligoquinoline TQB organic semiconductor DPA. A gram scale was also achieved Resonant Acoustic Mixing (RAM), providing an isolated yield 87% after simple recrystallization ethanol.

Language: Английский

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Ru-CNP Complex-Catalyzed Hydrogen Transfer/Annulation Reaction of 2-Nitrobenzylalcohol via an Outer-Sphere Mechanism

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 3, 2025

The development of efficient catalysts plays a central role in advancing chemical reactions. In this study, ruthenium complex modified with N-heterocyclic carbene-imine-phosphine ligand (CNP) was employed to enhance the hydrogen transfer/annulation process 2-nitrobenzyl alcohols various primary or secondary alcohols. NMR and HRMS analyses reaction solution revealed situ formation [fac-RuH(CO)(PPh3)(κ3-CN(H)P)]Cl through transfer hydrogenation imine moiety within CNP under conditions. This species, bifunctional Noyori-type featuring facial coordination CN(H)P ligand, served as key catalytic intermediate. By leveraging outer-sphere mechanism facilitated by [fac-RuH(CO)(PPh3)(κ3-CN(H)P)]Cl, synthesis 75 quinolines from wide range has been achieved yields high 95%.

Language: Английский

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<i>ortho</i>-Functionalized nitroarenes in the synthesis of heterocycles

Russian Chemical Reviews, Journal Year: 2025, Volume and Issue: 94(4), P. RCR5167 - RCR5167

Published: April 1, 2025

The development of convenient methods for the synthesis heterocyclic compounds that are highly important search pharmacological substances and in other spheres human activity is among most relevant fields organic chemistry. Two functional groups arenes located adjacent positions benzene ring can provide a fused ring. If at least one two <i>ortho</i>-functional contains nitrogen atom, heterocycle formed upon cyclization. nitro group often chosen as nitrogen-containing <i>ortho</i>-substituted to form systems, because ready availability <i>ortho</i>-functionalized nitroarenes, ability undergo various reactions selectivity reactions. This review integrates analyzes first time published data on involvement nitroarenes design structures. Using numerous examples reported literature last decade, mutually beneficial effect groups, which group, formation heterocycles demonstrated. Examples both intramolecular cyclizations involving additional reagents considered. gives holistic view potential functionalized <i>ortho</i>-nitroarenes systems. <br> bibliography includes 132 references.

Language: Английский

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Dinuclear Ru(II) Schiff Base Complex Catalyzed One-Pot Synthesis of Quinolines through Acceptorless Dehydrogenative Coupling of Secondary Alcohols with 2-Nitrobenzyl Alcohol

Organometallics, Journal Year: 2024, Volume and Issue: 43(10), P. 1190 - 1202

Published: May 10, 2024

Dinuclear Ru(II) complexes [(p-cymene)2(RuCl)2L1]2X (X = BF4 (Ru1); X PF6 (Ru2)) and mononuclear [(p-cymene)(RuCl)L2]BF4 (Ru3) (where L1 N,N′-(3,3′,5,5′-tetraisopropyl-[1,1′-biphenyl]-4,4′-diyl)bis(1-(pyridin-2-yl)methanimine); L2 N-(2,6-diisopropyl-phenyl)-1-(pyridin-2-yl)-methanimine) have been synthesized characterized by spectroscopic analytical techniques. Ru1 Ru2 orchestrate direct transformation of 2-nitrobenzyl alcohols to quinolines under mild conditions with significant efficiency even when employed at a minimal catalyst loading 0.1 mol %. Proportional experiments carried out the corresponding complex Ru3 keeping Ru content same (0.2 % Ru3) reveal superior activity bimetallic system for one-pot quinoline synthesis. Late-stage functionalization bioactive steroids scale-up synthesis demonstrate practical applicability present system. A probable mechanism this conversion is proposed based on trapping many intermediates ESI-mass spectroscopy. These mechanistic studies further substantiated ReactIR monitoring progress reaction in real time.

Language: Английский

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Accessing 2‐Aryl Quinolines via Acceptorless Dehydrogenation and Transfer Hydrogenation Under Base and Solvent‐Free Reaction Conditions

ChemistrySelect, Journal Year: 2023, Volume and Issue: 8(45)

Published: Dec. 1, 2023

Abstract Catalytic hydrogenation/dehydrogenation reactions are one of the most active areas research for synthesis pharmaceuticals and fine chemicals. Despite several efficient homogeneous catalysts that have already been identified, highly heterogeneous remain elusive. Herein, we report an easy convenient wet impregnation method Pd‐nanoclusters supported on ZnO nanoparticles. The catalyst displays a multifunctional role in 2‐aryl quinolines using alcohol 2‐nitrobenzyl as reactants via dehydrogenation/hydrogenation pathway under neat base‐free reaction conditions. exhibits excellent selectivity can be recycled five times without appreciable loss its activity.

Language: Английский

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A Chromium Catalytic System for the Synthesis of Aryl‐Substituted 1,3,5‐Triazines and Pyrimidines by Acceptorless Dehydrogenative Coupling

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 19, 2024

Abstract A novel and highly efficient method for the synthesis of 2,4,6‐triaryl‐1,3,5‐triazines 2,4,6‐trisubstituted pyrimidines from amidines alcohols has been established. Using an Earth‐abundant air‐stable chromium salt catalyst a phosphine‐free ligand, developed Cr‐catalyzed acceptorless dehydrogenative coupling provides 1,3,5‐triazines with high yields good functional group tolerance. Moreover, synthetic value this operationally simple protocol was demonstrated by gram‐scale experiment linker to construct various supramolecular complexes.

Language: Английский

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Six-membered ring systems: Pyridines and benzo analogs

Progress in heterocyclic chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 309 - 354

Published: Jan. 1, 2024

Language: Английский

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Synthesis and catalytic activity of POCOP ruthenium(II) and iron(II) pincer complexes derived from 1,3- and 1,7-dihydroxynaphthalenes

Journal of Coordination Chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 1 - 17

Published: Dec. 31, 2024

Ruthenium(II) and iron(II) POCOP pincer complexes have readily been obtained from ligands derived the 1,3- 1,7-dihydroxynaphtalene isomers. The two ruthenium(II) isomers displayed remarkable catalytic activity for Friedländer annulation, reaction was tolerant to a wide array of electron-withdrawing -donating substituted ketones. reactions produced selectively quinoline derivatives in conversions up 99% at low catalysts loadings with turnover numbers close 1000. iron also exhibited notable activity, albeit lower than their ruthenium counterparts. These results mark significant advancement developing derivatives.

Language: Английский

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