Tandem one-pot synthesis of 2-arylcinnolin-6-one derivatives from arylhydrazonopropanals and acetoacetanilides using sustainable ultrasound and microwave platforms

Several 2-arylcinnolin-6(2H)-one derivatives were synthesized via tandem annulation of a large number of 3-oxo-2-arylhydrazonopropanals with acetoacetanilide under three different heating modes (conventional heating, ultrasound and microwave irradiation) using triethylamine in ethanol. The factors affecting the optimization of the annulation process were thoroughly studied. The annulated structures were established on the basis of ¹H and ¹³C NMR and MALDI-TOF/MS spectral data as well as single crystal X-ray analysis.

Several 2-arylcinnolin-6(2H)-one derivatives were synthesized via tandem annulation of a large number of 3-oxo-2-arylhydrazonopropanals with acetoacetanilide under three different heating modes.     

Preparation of 3,5-diarylsubstituted 5-hydroxy-1,5-dihydro-2H-pyrrol-2-ones via base-assisted cyclization of 3-cyanoketones

A convenient preparative method is developed allowing for expeditious assembly of 3,5-diarylsubstituted 5-hydroxy-1,5-dihydro-2H-pyrrol-2-ones from routinely available inexpensive synthetic precursors. These compounds could not be prepared via the previously known protocols, as 2-aminofuran derivatives were produced instead.

The highly efficient oxidative cyclization of 1,3-diarylsubstituted 3-cyanoketones yielded 5-hydroxy-1,5-dihydro-2H-pyrrol-2-ones.     

Nitrileimines as an alternative to azides in base-mediated click [3 + 2] cycloaddition with methylene active nitriles

Nitrileimines were implemented in practical click protocols with oxopropanenitriles for the straightforward 5-amino-1H-pyrazole synthesis via 1,3-dipolar cycloaddition. The reaction proceeds at room temperature in a short time with base catalysis and no chromatographic purification. High purity products were isolated by simple filtration. The selectivity of the reaction was observed.

Nitrileimines were implemented in practical click protocols with oxopropanenitriles for the straightforward 5-amino-1H-pyrazole synthesis via 1,3-dipolar cycloaddition.     

Continuous-flow synthesis of 3,5-disubstituted pyrazoles via sequential alkyne homocoupling and Cope-type hydroamination

A flow chemistry-based approach is presented for the synthesis of 3,5-disubstituted pyrazoles via sequential copper-mediated alkyne homocoupling and Cope-type hydroamination of the intermediary 1,3-diynes in the presence of hydrazine as nucleophilic reaction partner. The proposed multistep methodology offers an easy and direct access to valuable pyrazoles from cheap and readily available starting materials and without the need for the isolation of any intermediates.

A telescoped continuous-flow method is presented for the synthesis of 3,5-disubstituted pyrazoles via copper-mediated alkyne homocoupling and Cope-type hydroamination of the intermediary 1,3-dialkynes.     

Urazolium diacetate as a new,efficient and reusable Brønsted acid ionic liquid for the synthesis of novel derivatives of thiazolidine-4-ones

Urazolium diacetate catalyzed synthesis of new derivatives of 1,3-thiazolidine-4-ones (azo dispersive dyes family) via multicomponent reaction of various aldehydes, thioglycolic acid and 4-aminoazobenzene under solvent-free reaction was reported. This avenue for the synthesis of new derivatives of thiazolidine-4-one has advantages as: short reaction times, high yields, green aspect of chemistry and environmental friendliness, easy workup, solvent-free conditions and convenient operation.

Urazolium diacetate catalyzed synthesis of new derivatives of 1,3-thiazolidine-4-ones (azo dispersive dyes family) via multicomponent reaction of various aldehydes, thioglycolic acid and 4-aminoazobenzene under solvent-free reaction was reported.     

1,3-Phenylene-bridged naphthalene wheels synthesized by one-pot Suzuki–Miyaura coupling and the complex of the hexamer with C60

A large 1,3-phenylene-bridged hexameric naphthalene wheel N6 and a heptameric wheel N7 were synthesized simply by Suzuki–Miyaura coupling via one-pot reaction from monomers. We could control the distribution of N6 and N7via the reaction conditions. The hexameric wheel structure was revealed by X-ray diffraction analysis. The wheel N6 exhibited C₆₀ encapsulation ability in the solid state, which was also confirmed by single crystal X-ray analysis.

1,3-Phenylene-bridged cyclic hexa-naphthalene synthesized by Suzuki–Miyaura coupling via a one-pot reaction formed a co-crystal with C₆₀ to exhibit a 1D alignment of fullerene.     

Efficient synthesis of ether phosphonates using trichloroacetimidate and acetate coupling methods

A series of ether phosphonates have been prepared by trichloroacetimidate and acetate coupling methods. Trichloroacetimidates or acetates were treated with primary and secondary alcohols as O-nucleophiles in the presence of catalytic TMSOTf to afford 21 examples of diethyl alkyloxy(substitutedphenyl)methyl phosphonates via C–O bond formation in 55–90% yields and short reaction time.

An efficient method for the synthesis of various ether phosphonates by trichloroacetimidate and acetate coupling methods is described.     

Preparation of polyimide films via microwave-assisted thermal imidization

A series of polyimide (PI) films based on aromatic heterocyclic monomers of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), p-phenylenediamine (p-PDA) and 4,4′-oxydianiline (ODA) were prepared via a microwave-assisted thermal imidization and conventional thermal imidization method at different temperatures. The effects of microwave irradiation on the imidization degree, microstructures, mechanical and thermal properties of PI films were investigated. The imidization degree of the PI films treated with microwave-assisted heating reached a relatively high value at 250 °C, which was twice as much as those treated with traditional thermal imidization. The tensile strength and modulus of PI films treated with microwave-assisted imidization at 300 °C were 187.61 MPa and 2.71 GPa respectively, which were 30% higher than those of PI films treated with thermal imidization. Moreover, the order degree of polymer chains was improved by the microwave-assisted imidization method. The PI films prepared by the microwave-assisted imidization method showed excellent thermal stability with a 5% weight loss temperature of 573 °C under N₂. The microwave-assisted thermal imidization proved to be a rapid and efficient way to prepare high-performance polyimide materials.

A series of polyimide films were prepared via a microwave-assisted thermal imidization and conventional thermal imidization method at different temperatures.     

Enhanced microwave absorption performance of light weight N-doped carbon nanoparticles

Microwave absorbents with specific morphology and structure have fundamental significance for tuning microwave absorption (MA). Herein, N-doped carbon sphere nanoparticles and hollow capsules were successfully fabricated via oxidative polymerization of dopamine in different mixed solutions, without any template preparation or etching process. Compared to solid particles, the microwave absorbents consisting of N-doped carbon with a hollow structure showed enormously enhanced MA performance, exhibiting a broad effective absorption bandwidth (from 12.7 GHz to 17.9 GHz) and a minimum reflection loss of −27.2 dB with a sample thickness of 2.0 mm. This work paves an attractive way for simple and eco-friendly preparation of advanced light weight microwave absorbents.

N-doped carbon particles were prepared through environmentally friendly and convenient methods. N-doped carbon capsules exhibit the best microwave absorption ability compared to their spherical counterparts.     

Highly selective cross-coupling reactions of 1,1-dibromoethylenes with alkynylaluminums for the synthesis of aryl substituted conjugated enediynes and unsymmetrical 1,3-diynes

A highly efficient method for the synthesis of aryl substituted conjugated enediynes and unsymmetrical 1,3-diynes via selective cross-coupling reactions of 1,1-dibromoethylenes with alkynylaluminums using the Pd(OAc)₂–DPPE and Pd₂(dba)₃–TFP complexes as catalysts, respectively, has been successfully developed. Though the alkyl substituted conjugated enediynes and unsymmetrical 1,3-diynes were not obtained, this case is also remarkable as the same starting materials could selectively produce either aryl substituted conjugated enediynes or unsymmetrical 1,3-diynes in moderate to excellent yields (up to 99%) in the different Pd–phosphine catalytic systems.

A highly efficient method for the synthesis of aryl substituted conjugated enediynes and unsymmetrical 1,3-diynes via selective cross-coupling reactions of 1,1-dibromoethylenes with alkynylaluminums has been successfully developed.     

Transition metal- and catalyst-free one-pot green method for the synthesis of N-sulfonyl amidines via direct reaction of sulfonyl azides with amines

In this report, a green synthesis of N-sulfonyl amidines via the direct reaction of tertiary or secondary amines with sulfonyl azides is described. Transition metal- and catalyst-free conditions were used for the synthesis of biologically important N-sulfonyl amidines. Further studies showed that the reaction proceeded via in situ aerobic oxidation of amines under reflux conditions.

A green synthesis of N-sulfonyl amidines via the direct reaction of tertiary or secondary amines with sulfonyl azides.     

Cu/TEMPO catalyzed dehydrogenative 1,3-dipolar cycloaddition in the synthesis of spirooxindoles as potential antidiabetic agents

A series of spiro-[indoline-3,3′-pyrrolizin/pyrrolidin]-2-ones, 4, 5 and 6 were synthesized in a sequential manner from Cu–TEMPO catalyzed dehydrogenation of alkylated ketones, 1 followed by 1,3-dipolar cycloaddition of azomethine ylides via decarboxylative condensation of isatin, 2 and l-proline/sarcosine, 3 in high regioselectivities and yields. The detailed mechanistic studies were performed to identify the reaction intermediates, which revealed that the reaction proceeds via dehydrogenative cycloaddition. Additionally, the regio and stereochemistry of the synthesized derivatives were affirmed by 2D NMR spectroscopic studies. The synthesized derivatives were explored further with molecular docking, in vitro antioxidant, and anti-diabetic activities.

A series of spiro-[indoline-3,3′-pyrrolizin/pyrrolidin]-2-ones were synthesized from Cu–TEMPO catalyzed dehydrogenation followed by 1,3-dipolar cycloaddition of azomethine ylides via decarboxylative condensation, resulting in high regioselectivities and yields.     

CuI nanoparticle-catalyzed synthesis of tetracyclic benzo[e]benzo[4,5]imidazo[1,2-c][1,3]thiazin-6-imine heterocycles by SNAr-type C–S,C–N bond formation from isothiocyanatobenzenes and benzimidazoles

In this paper, a simple and practical synthesis of benzo[e]benzo[4,5]imidazo[1,2-c][1,3]thiazin-6-imine tetracyclic heterocycles via a CuI nanoparticle-catalyzed intramolecular C(sp²)–S coupling reaction is presented. This strategy provides a straightforward method for synthesizing analogs of the anti-HIV drug 3,4-dihydro-2H,6H-pyrimido[1,2-c][1,3]benzothiazin-6-imine (PD 404182). The reaction rate and yield were increased by employing CuI nanoparticles.

We proposed a practical synthesis of analogs of the anti-HIV drug 3,4-dihydro-2H,6H-pyrimido[1,2-c][1,3]benzothiazin-6-imine via a CuI nanoparticle-catalyzed intramolecular C(sp²)–S coupling reaction.     

[3+2] regioselective annulation reaction of 2-arylidene-1,3-indandiones towards synthesis of spirocyclopentenes: understanding the mechanism of γ-attack vs. α-attack using DFT studies

A regioselective [3+2] cyclisation reaction between 2-arylidene-1,3-indanedione and ethyl 2,3-butadienoate catalysed by triphenylphosphine has been demonstrated to synthesize functionalised spirocyclic cyclopentenes. The reaction tolerated various electron-rich and electron-deficient aryl substituted 2-arylidene-1,3-indanediones with high to excellent chemical yields (up to 99%) and moderate to good regioselectivity (up to 5 : 1). DFT studies have also been carried out to understand the regioselective nature of this reaction. The results of Frontier molecular orbital calculations and the activation energy (E_a) favour the formation of compound 3avia γ-attack compared to that of 4avia α-attack.

A [3+2] annulation protocol for the construction of functionalized spirocyclopentenes utilizing 1,3-indanedione derived benzylidene-1,3-indanedione and ethyl-2,3-butadienoate at room temperature was developed.     

Thioether-functionalized trifluoromethyl-alkynes, 1,3-dienes and allenes: divergent synthesis from reaction of 2-trifluoromethyl-1,3-conjugated enynes with sulfur nucleophiles

A divergent synthesis of thioether-functionalized trifluoromethyl-alkynes, 1,3-dienes and allenes via regioselective nucleophilic addition of sulfur nucleophiles to 2-trifluoromethyl-1,3-conjugated enynes was developed. The addition patterns depend on the type of enyne, sulfur nucleophile and reaction conditions used. 1,4-Addition leading to thioether-functionalized trifluoromethyl-allenes was realized when enynes possessing electron-withdrawing aryl groups on the alkyne moiety were used as reaction partners and alkanethiols were used as nucleophiles, whereas solvent-controlled construction of thioether-functionalized 1,3-dienes and alkynes was realized, respectively, via a 3,4-addition pattern or 1,2-addition pattern if thiophenols were applied as nucleophiles. The three types of compounds containing both sulfur and fluorine elements are valuable building blocks for synthesis of multifunctional fluorinated vinyl sulfides and thiophene derivatives.

A divergent synthesis of thioether-functionalized trifluoromethyl-alkynes, 1,3-dienes and allenes viaregioselective nucleophilic addition of sulfur nucleophiles to 2-trifluoromethyl-1,3-conjugated enynes was developed.     

CuI nanoparticles supported on a novel polymer-layered double hydroxide nanocomposite: an efficient heterogeneous nanocatalyst for the synthesis of bis-N-arylsulfonamides

A new type of polymer-layered double hydroxide nanocomposite bearing thiazole moieties was used to support CuI nanoparticles (NPs) as a heterogeneous catalyst for the synthesis of bis-N-arylsulfonamides. The prepared nanostructured catalyst (LDH@MPS-GMA-TZ-CuI) showed high catalytic activity, as well as excellent recyclability for the preparation of bis-N-arylsulfonamides via the chemoselective reaction of 1,3-disulfonyl chloride and nitroarenes. The superior catalytic activity of the LDH@MPS-GMA-TZ-CuI is related to the high loading of CuI NPs and favorable surface properties.

CuI NPs supported on novel polymer–LDHs nanocomposite was investigated for the synthesis of bis-N-arylsulfonamides.     

49.25% efficient cyan emissive sulfur dots via a microwave-assisted route

Cyan emissive sulfur dots with a record high photoluminescence (PL) quantum yield of 49.25% have been successfully prepared via a microwave-assisted top-down route. The PL enhancement induced by electrostatic repulsion of sulfite groups and steric hindrance of polyethylene glycol 400 (PEG-400) were investigated for the first time.

The cyan emissive sulfur dots with a record high PL QY of 49.25% were successfully synthesized via a microwave-assisted route.     

Macrocyclic pentamers functionalised around their periphery as potential building blocks

The elaboration of a five-fold symmetric macrocyclic aromatic pentamer bearing peripheral benzyloxy and hydroxyl groups is described. These could be used to explore further functionalisation for use as pentagonal building blocks. The internal fluorine-substituted macrocycle has been prepared via a one-pot procedure which is an improvement on the stepwise chain growth approach reported in the literature.

The elaboration of a five-fold symmetric macrocyclic aromatic pentamer bearing peripheral benzyloxy and hydroxyl groups is described. The macrocycle bearing internal fluorine substituents has been prepared via a one-pot procedure.     

Synthesis of a hierarchical carbon fiber@cobalt ferrite@manganese dioxide composite and its application as a microwave absorber

In this study, a novel hierarchical carbon fiber@cobalt ferrite@manganese dioxide (CF@CoFe₂O₄@MnO₂) composite was facilely prepared via a sol–gel method and hydrothermal reaction. The morphology, structure, chemical and element composition, crystal form, elemental binding energy, magnetic behavior and microwave absorbing performance of the composite were carefully investigated. According to its hysteresis loops, the composite exhibits a typical soft magnetic behavior, with a M_s value of 30.2 emu g⁻¹. Besides, the as-synthesized CF@CoFe₂O₄@MnO₂ composite exhibits superior microwave absorption performance mainly due to reasonable electromagnetic matching, and its minimum reflection loss value can reach −34 dB with a sample thickness of just 1.5 mm. The composite can be regarded as an ideal microwave absorber.

In this study, a novel hierarchical carbon fiber@cobalt ferrite@manganese dioxide (CF@CoFe₂O₄@MnO₂) composite was facilely prepared via a sol–gel method and hydrothermal reaction.     

Environmentally friendly domino multicomponent strategy for the synthesis of pyrroloquinolinone hybrid heterocycles

An efficient and elegant assembly of pyrene/aryl fused pyrrolo[2,3-b]quinolinone and pyrrolizino[3,2-b]quinolinone hybrid heterocycles was achieved via a domino multicomponent reaction strategy using a solid state melt reaction (SSMR) condition. The 1,3-dipole component was generated in situ from N-methylgylcine/l-proline and isatin, while the Baylis–Hillman adduct prepared from pyrene-1-carbaldehyde and various benzaldehydes is used as the dipolarophile. The domino protocol comprises 1,3-dipolar cycloaddition and a consequent double annulation reaction process. The advantages of this cascade protocol include environmentally friendly conditions, the avoidance of toxic organic solvents, simple work-up and good to excellent product yields.

An efficient and elegant assembly of pyrene/aryl fused pyrrolo[2,3-b]quinolinone and pyrrolizino[3,2-b]quinolinone hybrid heterocycles was achieved via a domino multicomponent reaction strategy using a solid state melt reaction (SSMR) condition.