<i>β</i>-Oxoanilides in Heterocyclic Synthesis: Synthesis and Antimicrobial Activity of Pyridines, Pyrans, Pyrimidines and Azolo, Azinopyrimidines Incorporating Antipyrine Moiety

Condensation of β-Oxoanilide 1 with active methylene derivatives 2a,bafforded the pyridine derivative 5, and with crotononitrile afforded the pyridine 8. Compounds 9 and 11a-c were obtained by reaction of 1 with malononitrile dimer and arylidinemalononitrile 10a-10c. In contrast, when compound 1 reacted with ethoxymethylen malononitrile afforded the pyridine derivative 13. On the other hand, treatment of 1 with anthranilic acid gave the quinoline derivative 14. Also, reactions of 1 with isothiocyanate derivatives afforded compounds 16-18. The reaction of 1 with chalcone derivative afforded the pyridine derivative 22. Treatment of compound 1 with thiourea produced pyrimidine derivative 23. Furthermore, compound 1 converted into pyrimidinethione 24a and pyrimidinone 24b on treatment with a mixture of aromatic aldehydes and thiourea or urea respectively. Reaction of 24a with hydrazonyl halide, thiosemicarbazide and arylidinecyanothioacetamide afforded compounds 26, 28 and 29. Compound 29 was treated with chloroacetonitrile to afford compound 30. Six compounds from the newly synthesized were screened for antibacterial and antifungal activity against bacteria staphylococcus aureus, bacillus cereus and klebsiella pneumonia and fungi aspergillus flavus and aspergillus ochraceous, respectively. Some of the tested compounds showed significant antimicrobial activity. IR, 1H NMR, mass spectral data, and elemental analysis elucidated the structures of all the newly synthesized compounds.

Heterosynthesis Using Nitriles: Novel Pyrrolo[2,3-<i>b</i>]pyridines

2-Amino-4-benzoyl-1-arylpyrrole-3-carbonitriles react with arylidene malonodinitriles, β-ketoesters and β- diketones to afford pyrrolo[2,3-b]pyridine derivatives.

One-Pot Three-Component Synthesis of Imidazo[1,5-<i>a</i>]pyridines

A one-pot three component condensation synthesis of imidazo[1,5-a]pyridines using of various aromatic aldehydes and dipyridil ketone with ammonium acetate in the presence of Lithium chloride as catalyst in good yields under microwave irradiation has been described.

Efficient Synthesis of Dicycloalkenopyridines:One-pot Multicomponent Condensation of Aldehydes with Cyclic Ketones

Under microwave irradiation, the one-pot multicomponent condensation reaction of three moles of aromatic aldehydes with two moles of cyclic ketones having free a,a＇-methylene positions such as cyclopentanone or cyclohexanone in the presence of ammonium acetate and acetic acid afforded dicycloalkenopyridines with two a-arylidene groups in high yields. Under the similar reaction condition, the reaction of aromatic aldehydes with 1-tetralone having only one a-methylene position alternatively resulted in 10-aryl-2,3：5,6-dibenzoacridines.

Synthesis of 2,4-Diarylcyclooctenopyridines with One-pot Four-component Reactions

An efficient one-pot four-component reaction has been developed for the synthesis of 2,4-diarylcyclooctenopyridines, in moderate yields. This route is an effective modified two-step synthesis of Krohnke pyridine and involves a four-component tandem reaction of pyridinium bromide with aromatic aldehydes and cyclooctanone in a system of NHaOAc/HOAc under microwave irradiation.

Some Transition Metal Complexes Bearing Artemisinin Derivatives and （N-N-O） Tridentate Chromium （Ⅲ） Complexes Ligated by 2-benzolmidazo-yl-6-acetyl. pyridines for Catalytic Behaviour towards Ethylene

Interventions of metal complexes in the area of metallopharrneceutical and polymer sciences play a great economic importance to human challenges. Complexation behavior of some artemisinin derivatives with late transition metals and chromium-benzoimidazoylpyridine analogues have been investigated. The Fe（Ⅲ）, Zn（Ⅱ） and Cd（Ⅱ） complexes of artesunate and artemether and that of chromium-benzimidazoyl pyridine were synthesized with molar ratio of metal to ligand between 1：1 and 1：2. Structural elucidation using X-ray analysis and other characterization of the complexes （AAS, IR, UV, E.A, NMR） were carried out to explore the coordination affinity of them viz-a viz bonding, geometries and elemental composition. The IR absorption revealed that artesunate acts as monodentate specie through carbonyl group on coordination. However, its bidentate mode was also observed with carboxylic group acting as C=O and C-O bonding when deprotonation happened. Artemether （L2） was synthesized using artesunate and its structure was confirmed by single crystal X-ray crystallography as well as its Zn（Ⅱ） complex exhibiting a square planar geometry. A series of 2-benzoimidazoylpyridine derivates （L3-L6） and their chromium complexes were synthesized and characterized. In the presence of methylaluminoxane （MAO）, all chromium complexes show good activity for ethylene oligomerization and polymerization whereas with diethylaluminium chloride （Et2AlCl2） the complexes show moderate activity. The distribution of oligomers obtained follows Schulz- Flory rules with high selectivity for α-olefins. The combined productivity （meaning both activities of ethylene oligomerization and polymerization） are improved with increasing ethylene pressure. The results show that the reaction conditions greatly affect the properties of the polymer such as molecular weight distribution and melting point（Tm） with extremely broad molecular weight distributions. With elevating reaction temperature from 0 to 60 ℃, the melting point （Tin） of resultant polyethylene decreased rapidly from 134 ℃ to 70 ℃.

Microwave-prompted rapid and efficient synthesis of 3-alkyl substituted imidazo[1,5-a]pyridines

Under regular heating and microwave irradiation, 3-alkyl substituted imidazo[1,5-a] pyridines were synthesized from 2,2＇- pyridil, di-2-pyridyl ketone and aliphatic aldehydes in the presence of ammonium acetate and acetic acid. Compared to the traditional heating condition, the reaction time under microwave irradiation was shorter and 3-alkyl imidazo[1,5-a]pyddines were given in higher yield.

Living/controlled polymerization of vinylpyridines into sequence-regulated copolymers by Lewis pair

The poly(vinylpyridine)(PVP) based(co)polymers are of particular interest in materials science, due to their multifunctionality and diverse applications. So far, there is no report on the sequence-regulated copolymerization of vinylpyridines(VPs) and methacrylate monomer in one-step manner yet. Here we designed and synthesized a series of guanidine phosphines as Lewis base(LB), which is combined with bulky organoaluminium to construct Lewis pairs(LPs) for polymerization of VPs. The living/controlled polymerization of 4-vinylpyridine(4-VP) or 2-vinylpyridine(2-VP) can be accomplished with remarkable efficiency by such Lewis pair polymerization(LPP), furnishing polymers with high molecular weight(up to 288 kg/mol) and narrow molecular weight distribution(as low as 1.17). Mechanistic studies reveal the interaction of LPs and formation of zwitterionic intermediates, providing solid evidences to support the proposed polymerization mechanism. More importantly, by simply adjusting the LA dosage, this LPP strategy realizes the unprecedented control over the sequence regulation of 2-VP-based copolymers from gradient to block in one-step manner, regardless of the monomer ratio, which greatly expands the versatility of the LPP.

Supported Recyclable Metal-free Frustrated Lewis Pair Catalyst for Catalytic Hydrogenation of Substituted Pyridines to Piperidines

The construction of heterogeneous frustrated Lewis pairs(FLPs)catalysts is crucial for realizing highly efficient and recyclable pyridines catalytic hydrogenation.In this work,we prepared a recyclable heterogenous FLPs catalyst CMP-BF with conjugated microporous polymer CMP-ethynyl as the support via self-catalyzed 1,1-carboboration reaction with commercial Lewis acid B(C_(6)F_(5))_(3).The as-synthesized CMP-BF demonstrates superior heterogenous catalytic hydrogenation performance(conversion>99%),and considerable stability(84%conversion after three cycles)in recyclable hydrogenation of 2,6-phenylpyridine.This work provides insights into the fabrication and catalytic application of recyclable heterogenous FLP catalysts.

Iodomethane as an organocatalyst for the aerobic ortho-selective trifluoromethylation of pyridines

Iodomethane is usually used as an electrophilic methylation reagent.Herein,we report its use as a C1 organocatalyst for the aerobic ortho-selective trifluoromethylation of pyridines in the absence of a transition metal.Trifluoroacetic acid(TFA)was employed as an inexpensive,readily available trifluoromethyl source.The reaction efficiently produced a variety of trifluoromethylation products,with good functional group compatibility.Pyridine-containing drug molecules could also be selectively trifluoromethylated for late-stage functionalizations.Mechanistic studies showed that iodomethane selectively reacted with the pyridine starting material,rather than the pyridine product,to generate the corresponding N-methylpyridinium iodide.The decarboxylation of trifluoroacetic acid produced a trifluoromethyl anion,which added to the methylpyridinium iodide,and the subsequent aerobic rearomatization led to the generation of the ortho-trifluoromethylated product.

Visible Light-Induced C-5 Selective C-H Radical Borylation of Imidazo[1,2-a]pyridines with NHC-Boranes

A visible-light-induced C-5 selective C-H borylation of imidazo[1,2-a]pyridines with NHC-BH3 via Minisci-type radical borylation re-action has been developed for the first time.The present sustainable protocol provides a new family of regioselectively C5-borylated imidazopyridines that would otherwise be difficult to prepare.It is a supplement to site-selective borylation of azines(nitrogen-con-taining aromatic heterocycles)and the assembly of sp2 carbon-boron bond.

C–H alkylation of pyridines with olefins catalyzed by imidazolin-2-iminato-ligated rare-earth alkyl complexes

An array of rare-earth bis(aminobenzyl)complexes supported by imidazolin-2-iminato ligands were synthesized and structurally characterized.These complexes showed high activity towards ortho-Csp^(2)–H alkylation of 2-alkylpyridines and benzylic Csp^(3)–H alkylation of 2,6-dialkylpyridines with alkenes.A wide range of alkyl or aryl substituted olefin substrates are compatible,providing an atom-economical route to linear or branched alkylated pyridine derivatives in moderate to high yields(45 examples,up to 99%yield).The primary study suggested that the asymmetric version of Csp^(3)–H alkylation of 2,4,6-collidine with allylbenzene was feasible with chiral imidazolin-2-iminato-ligated scandium(III)complexes,and good yield with moderate enantioselectivity was obtained(84%yield,84:16 er).Mechanistic investigations including kinetic isotope effect(KIE)experiments and density functional theory(DFT)calculations shed light on the catalytic cycle and the origin of enantiocontrol.

Direct benzylic functionalization of pyridines:Palladium-catalyzed mono-α-arylation of α-(2-pyridinyl)acetates with heteroaryl halides

Herein,we report a Pd-catalyzed mono-a-arylation reaction for pyridine benzylic functionalization.This approach serves as an efficient alternative to synthesize di-heteroaryl acetates in good yields and selectivities.Moreover,the method is applicable to heteroa ryl substrate combinations,and exhibits great functional group tolerance.A streamlined protocol also enables the rapid synthesis of diheteroaryl ketones.The synthetic value was also demonstrated by scale-up experiments.

Regioselective Synthesis of Fused Azo-linked Pyrazolo[4,3-e]pyridines Using Nano-Fe3O4

A multicomponent reaction for the synthesis of fused azo-linked pyrazolo[4,3-e]pyridines from 3-amino-5-methylpyrazole, indan-l,3-dione and synthesized azo-linked aldehydes using nano-Fe304 as an effective and reusable catalyst is reported. The present methodology offers several advantages, such as a simple procedure with an easy work-up, short reaction times, high yields, and the absence of any volatile and hazardous organic sol- vents.

Enhanced stability of nitrogen-doped carbon-supported palladium catalyst for oxidative carbonylation of phenol

Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticles(NPs)on nitrogen-doped carbon;synthesized by using F127 as a stabilizer,as well as chitosan as a carbon and nitrogen source.The Pd/NCF catalyst was efficient and recyclable for oxidative carbonylation of phenol to diphenyl carbonate,exhibiting higher stability than Pd/NC prepared without F127 addition.The hydrogen bond between chitosan(CTS)and F127 was enhanced by F127,which anchored the N in the free amino group,increasing the N content of the carbon material and ensuring that the support could provide sufficient N sites for the deposition of Pd NPs.This process helped to improve metal dispersion.The increased metal-support interaction,which limits the leaching and coarsening of Pd NPs,improves the stability of the Pd/NCF catalyst.Furthermore,density functional theory calculations indicated that pyridine N stabilized the Pd^(2+)species,significantly inhibiting the loss of Pd^(2+)in Pd/NCF during the reaction process.This work provides a promising avenue towards enhancing the stability of nitrogen-doped carbon-supported metal catalysts.

Boosting Fischer-Tropsch Synthesis via Tuning of N Dopants in TiO_(2)@CN-Supported Ru Catalysts

Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such as Fischer-Tropsch synthesis(FTS).Herein,we engineered ruthenium(Ru)FTS catalysts supported on N-doped carbon overlayers on TiO_(2)nanoparticles.By regulating the carbonization temperatures,we successfully controlled the types and contents of N dopants to identify their impacts on metal-support interactions(MSI).Our fi ndings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species.Moreover,pyridinic N demonstrates the highest electron-donating ability,followed by pyrrolic N and graphitic N.In addition to realizing excellent catalytic stability,strengthening the interaction between Ru sites and N dopants increases the Ru^(0)/Ru^(δ+)ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO.Consequently,it improves the catalyst’s overall performance,encompassing intrinsic and apparent activities,as well as its ability for carbon chain growth.Accordingly,the as-synthesized Ru/TiO_(2)@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C_(5+)time yield of 219.4 mol CO/(mol Ru·h)and C_(5+)selectivity of 85.5%.

Lignin‐derived carbon with pyridine N‐B doping and a nanosandwich structure for high and stable lithium storage

Biomass‐derived carbon is a promising electrode material in energy storage devices.However,how to improve its low capacity and stability,and slow diffusion kinetics during lithium storage remains a challenge.In this research,we propose a“self‐assembly‐template”method to prepare B,N codoped porous carbon(BN‐C)with a nanosandwich structure and abundant pyridinic N‐B species.The nanosandwich structure can increase powder density and cycle stability by constructing a stable solid electrolyte interphase film,shortening the Li^(+)diffusion pathway,and accommodating volume expansion during repeated charging/discharging.The abundant pyridinic N‐B species can simultaneously promote the adsorption/desorption of Li^(+)/PF_(6)^(−)and reduce the diffusion barrier.The BN‐C electrode showed a high lithium‐ion storage capacity of above 1140 mAh g^(−1)at 0.05 A g^(−1)and superior stability(96.5%retained after 2000 cycles).Moreover,owing to the synergistic effect of the nanosandwich structure and pyridinic N‐B species,the assembled symmetrical BN‐C//BN‐C full cell shows a high energy density of 234.7Wh kg^(−1),high power density of 39.38 kW kg−1,and excellent cycling stability,superior to most of the other cells reported in the literature.As the density functional theory simulation demonstrated,pyridinic N‐B shows enhanced adsorption activity for Li^(+)and PF_(6)^(−),which promotes an increase in the capacity of the anode and cathode,respectively.Meanwhile,the relatively lower diffusion barrier of pyridinic N‐B promotes Li^(+)migration,resulting in good rate performance.Therefore,this study provides a new approach for the synergistic modulation of a nanostructure and an active site simultaneously to fabricate the carbon electrode material in energy storage devices.

Theoretical Investigation on the Stability and Reactivity of Imidazo [1,2-a] Pyridine N-Acylhydrazone Derivatives Using Density Functional Theory

The reactivity and stability of seventeen (17) imidazo [1,2-a]pyridine N-acylhydrazone derivatives were investigated using density functional theory at the B3LYP/6-31+ G (d, p) level. Analysis of the molecular electrostatic potential (MEP) and determination of the dual descriptor revealed that in most cases, the nitrogen atoms of the 6-πelectron conjugation, the oxygen, and the sulfur atom are nucleophilic site. Chemical reactivity of the compounds was assessed through analysis of frontier molecular orbitals (HOMO and LUMO), energy gap (Δℰ), chemical hardness (η), and the softness (S). Consequently, the compound 9e exhibited the lowest reactivity, least electron donating, and the highest stability. This comprehensive study offers valuable insights into the chemical behavior of these derivatives, crucial for further exploration and potential applications.

Transition-metal-switchable divergent synthesis of nitrile-containing pyrazolo[1,5-a]pyridines and indolizines

Palladium-catalyzed oxidative formal [4 + 1] annulation of pyridine-substituted acrylonitriles toward divergent fused N-heterocycles synthesis is reported. The heterodifunctionalization reaction with Cu(OAc);and urea as the nitrogen source accesses to nitrile-substituted pyrazolo[1,5-a]pyridines in moderate to good yields, while the homodifunctionalization reaction with FeBr;leads to synthesis of nitrilesubstituted indolizines in excellent yields.

Access to pyridines via cascade nucleophilic addition reaction of 1,2,3-triazines with activated ketones or acetonitriles

We studied the cascade nucleophilic addition reactions of 1,2,3-triazines with activated acetonitriles or ketones,which were used to construct highly substituted pyridines that are not easily accessed by conventional methods.The strategy addressed some structural diversity issues currently facing medicinal chemistry,and the resulting pyridines could be used as convenient precursors for the synthesis of related pharmaceuticals.In particular,our method was applied to the syntheses of the marketed drug etoricoxib and several biologically important molecules in a few steps.