Highly efficient copper(0)-catalyzed Suzuki-Miyaura cross-coupling reactions in reusable PEG-400

Readily available copper powder with K₂CO₃ as the base was extremely effective catalyst for Suzuki-Miyaura coupling reaction performed in PEG-400, which afforded almost quantitative coupling products of aryl iodides. Using iodine as additive, coupling products of aryl bromides or chlorides could be obtained with moderate to good yields.     

PEG-400-H2O as a green and recyclable medium for asymmetric hydrogenations of aromatic ketones catalyzed by RuCl2(TPPTS)2-(S,S)-DPENDS

PEG-400-H₂O was found to be a green and recyclable reaction medium for asymmetric hydrogenations of aromatic ketones catalyzed by a ruthenium achiral monophosphine complex RuCl₂(TPPTS)₂ [TPPTS: P(m-C₆H₄SO₃Na)₃] modified by (S,S)-DPENDS [disodium salt of sulfonated (S,S)-1,2-diphenyl-1,2-ethylene-diamine]. The acetophenone product was obtained with 86.3% ee under the optimized conditions. The resulting products can be easily separated from the catalyst by extraction with n-hexane. The catalyst immobilized in PEG-400-H₂O not only exhibits excellent activity and enantioselectivity, but also can be recycled and reused several times without a loss of activity or enantioselectivity.     

A highly efficient and recyclable NiCl2(dppp)/PEG-400 system for Suzuki-Miyaura reaction of aryl chlorides with arylboronic acids

Abstract

NiCl₂(dppp) in PEG-400 is shown to be a highly efficient catalyst for Suzuki-Miyaura coupling of aryl chlorides with arylboronic acids. The reaction could be conducted at 100?°C using K₃PO₄ as base, yielding a variety of biaryls in good to excellent yields. The isolation of the products was readily performed by extraction with petroleum ether and NiCl₂(dppp)/PEG-400 system could be easily recycled and reused up to five times without significant loss of activity. Our system not only avoids the use of easily volatile and toxic dioxane or toluene as a solvent but also solves the basic problem of nickel catalyst reuse.     

Microwave-promoted <Emphasis Type="Italic">N</Emphasis>-arylation of imidazole and amino acids in the presence of Cu<Subscript>2</Subscript>O and CuO in poly(ethylene glycol)

Copper(I)-catalyzed N-arylation of imidazole with iodobenzene, its derivatives, and bromobenzene in poly(ethylene glycol) under microwave irradiation was studied. The influence of the following factors on the yield of arylation product was investigated: the nature of the source of copper and ligand, type of poly(ethylene glycol) (PEG) used, and substituents in iodoarene. An optimal catalytic system was selected: CuO/l-Hys/Cs₂CO₃/PEG-400, a possibility of recycling of copper-containing catalyst was demonstrated. N-Arylation of eight natural amino acids using catalysis with Cu₂O/Cs₂CO₃/PEG-400 and microwave irradiation was studied, the dependence of the reaction results on temperature, duration of the process, and the ratio of the starting reagents was found. The highest yields of the target products were reached in the case of leucine, valine, and phenylalanine.     

PEG-400 promoted Pd(OAc)2/DABCO-catalyzed cross-coupling reactions in aqueous media

PEG-400 [poly(ethylene glycol-400)] was found to improve the Pd(OAc)₂/DABCO-catalyzed aqueous Suzuki-Miyaura and Stille cross-coupling reactions. In the presence of Pd(OAc)₂, DABCO, and PEG-400, a variety of aryl halides were coupled with arylboronic acids or organotin compounds efficiently to afford the corresponding cross-coupled products in moderate to excellent yields. The turnover numbers was up to 900,000 for the Suzuki-Miyaura reaction and up to 9800 for the Stille reaction. The catalyst system was also effective for Heck and Sonogashira cross-coupling reactions to some extent.     

Surfactant assisted zinc doped tin oxide nanoparticles for supercapacitor applications

Zinc doped tin oxide nanoparticles were synthesized by employing sol–gel method assisted with different surfactants namely cetyl trimethyl ammonium bromide (CTAB), hexamine and polyethylene glycol 400 (PEG-400). The synthesis of uniform distribution of spherical Zn-SnO₂ nanoparticles in presence of PEG-400 was optimized. The synthesized Zn-SnO₂ nanoparticles were characterized by employing standard characterization techniques. X-ray diffraction results confirmed the product high-quality crystalline formation. The photoluminescence peaks appeared at 360?nm revealed the recombination of electron and hole from band to band emission of SnO₂ optical properties. The vibrational properties of Zn-SnO₂ nanoparticles were confirmed by both Raman and infra red spectra. The spherical morphology and nano sized product was evident in 200?nm scale SEM images. The cyclic voltammetry result of the product Zn-SnO₂ assisted PEG-400 exhibited the specific capacitance value of 312.7?F/g at scan rate of 10?mV/s and revealed the superior electrochemical properties. Moreover, the EIS and GCD studies also revealed the good supercapacitor nature with specific capacitance of 132.1?F/g at current density of 1?A/g for the product Zn-SnO₂ (PEG-400).

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Diagrammatic representation of Zn doped SnO₂ synthesis by sol-gel method with enhanced specific capacitance of 132.1?F/g at 1?A/g for Zn-SnO₂ (PEG-400).

     

Synthesis of (Z)-organylthioenynes using KF/Al2O3/solvent as recyclable system

PEG-400 and glycerol were successfully used as recyclable solvents for the synthesis of several organylthioenynes in good to excellent yields and high selectivity using solid supported catalyst (KF/Al₂O₃). This easy, general and improved method furnishes the corresponding alkenyl sulfides preferentially with Z configuration. The catalytic system and the glycerol or PEG-400 can be reused up to three times without previous treatment with comparable activity.     

Novel copper/PEG-400 catalyst systems for chemoselective S- and N-arylation of 2-mercaptobenzothiazole

A novel approach for chemoselective S- and N-arylation of 2-mercaptobenzothiazole was developed by copper/PEG-400 catalyst systems. Copper source and reaction temperature play an important role in this protocol, selective S-arylation of 2-mercaptobenzothiazole was achieved by using CuI/PEG-400/50 °C catalyst system, while selective N-arylation was achieved with CuO/PEG-400/140 °C catalyst system. Both are compatible with a variety of aryl halides and selectively give the desired S- and N-arylation products in good to excellent yields, respectively.     

“Green synthesis” of benzothiazepine library of indeno analogues and their in vitro antimicrobial activity

A novel series of indeno-benzothiazepine derivatives was synthesised via a “green” route. Synthesis of these compounds involves the treatment of dinucleophiles such as 2-aminobenzenethiols with α,β-unsaturated ketones in poly(oxyethylene) (poly(ethylene glycol), PEG-400) catalysed by acetic acid. The synthone α,β-unsaturated ketones were obtained by Claisen-Schmidt condensation of indan-1-one with substituted pyrazole-2-carbaldehydes prompted by bleaching earth (pH 12.5) as catalyst and PEG-400 as “green” reaction solvent. Screening of all the synthesised compounds for antimicrobial activity revealed that most of these compounds exhibited moderate to significant antimicrobial activity.     

Guanidine complex of copper supported on boehmite nanoparticles as practical,recyclable, chemo and homoselective organic–inorganic hybrid nanocatalyst for organic reactions

Boehmite (BO) nanoparticles (NPs) were prepared via the injection of aqueous NaOH solution to aqueous aluminum nitrate solution at room temperature. Afterwards, a new complex of copper was immobilized on BO-NPs (Cu-Guanidine@BO-NPs). This heterogeneous nanocatalyst was used as a practical, recyclable, chemo and homoselective nanocatalyst in the organic processes, i.e. the preparation of tetrazole five-membered heterocycles and chemoselective sulfoxidation of sulfides using H₂O₂ as oxidant. In this sense, the prepared nanocatalyst was characterized by AAS, N₂ adsorption–desorption isotherms, WDX, EDS, SEM, and TGA techniques. The reusability of this catalyst was investigated in the described organic reactions for several runs without notable loss of its catalytic activity. Moreover, all of the tetrazole and sulfoxide derivatives were isolated in high Turn Over Number (TON) and Turn Over Frequency (TOF) numbers indicating the high activity and selectivity of Cu-Guanidine@BO-NPs in the described reactions.     

Mass-spectrometric study of the formation of silver nanoclusters in polyether media: 2. Fast atom bombardment and modeling

Within the problem of the synthesis of silver nanoclusters and nanoparticles in polyether media, systems containing silver nitrate AgNO₃ and low-molecular-weight polyethers, poly(ethylene glycol) PEG-400 or oxyethylated glycerol OEG-5, were studied by fast atom bombardment (FAB) mass spectrometry. The formation of stable clusters of polyether oligomers (M _m ) with silver cations M _m · Ag⁺ was shown, in agreement with the previous data of laser desorption/ionization. Quantum-chemical DFT calculations have shown that the M _m · Ag⁺ clusters are stabilized by wrapping of the polyether chain around the silver cation with the cation coordinating ether oxygen atoms. Silver nanoclusters were not found in the FAB mass spectra of liquid systems, but Ag _n ⁺ clusters were detected for silver nanoparticles separated from the reaction medium. No products of chemical transformations of PEG-400 or OEG-5 were observed by FAB. A plausible mechanism of the reduction of silver cations involving nitrate anions is discussed.     

超临界二氧化碳中功能化聚乙二醇稳定的钯纳米粒子催化醇的选择氧化反应

 以超临界二氧化碳 (scCO2)/聚乙二醇 (PEG) 两相为反应介质, 双齿氮配体功能化聚乙二醇稳定的 Pd 纳米颗粒作为催化剂, 进行了醇的需氧氧化反应. 系统研究了催化剂制备条件和反应条件对苯甲醇需氧氧化反应的影响. 结果表明, 以氢气为还原剂制备的 Pd 纳米粒子的催化活性最高. 反应结束后, 可以利用 scCO2 直接进行原位萃取得到产物, 实现了催化剂与产物的有效分离和催化剂的循环使用. 反应中没有检测到钯的流失. 催化剂经过 5 次循环利用后转化率仍可达 98%.     

Highly dispersed copper/ppm palladium nanoparticles as novel magnetically recoverable catalyst for Suzuki reaction under aqueous conditions at room temperature

An efficient procedure based on arginine‐modified Fe₃O₄@carbon magnetic nanoparticles (FCA MNPs) with highly dispersed copper nanoparticles (Cu NPs) and 92.8 ppm of Pd is reported for room temperature Suzuki reaction. For enhancing the activity of this Cu‐based heterogeneous catalyst, special arginine amino acid as a ligand with high content of heteroatoms was immobilized onto the Fe₃O₄@carbon MNPs to increase the electron density. Cu(II) ions were then loaded on the surface of the FCA MNPs and reduced to achieve uniformly dispersed Cu NPs. An aqueous mixture of metal hydroxides such as KOH, Ba(OH)₂, Ca(OH)₂, Mg(OH)₂ as a green, non‐toxic and basic medium was used for the Suzuki reaction at room temperature. This catalyst could also be recovered and reused with no loss of activity over six successful runs.     

热处理及反应介质对Cu-Zn-Al催化剂的结构及CO加氢催化性能的影响

催化剂的形成和使用环境对催化剂的结构和性能会产生重要的影响。本文采用完全液相法,以PEG-400和液体石蜡分别作为热处理介质制备Cu-Zn-Al催化剂,用X射线粉末衍射、H2程序升温还原、N2吸附、X射线光电子能谱对其进行表征,考察热处理介质对催化剂结构的影响;以相应的热处理介质作为浆态床反应介质,考察介质对CO加氢催化反应性能的影响。结果表明,PEG-400作为热处理介质有助于提高催化剂的比表面积、ZnO的分散度和表面铜含量,催化剂中存在难还原的Cu ,有利于形成Cu -Cu0之间的协同作用;在反应过程中,PEG-400作为反应介质可以抑制铜晶粒的长大,有利于乙醇的生成及C5烃选择性的提高,但催化剂的结构和表面组成会发生较大的变化。     

Shape-dependent catalytic activity of copper oxide-supported Pd(0) nanoparticles for Suzuki and cyanation reactions

Palladium nanoparticles supported on different shapes of nanocrystalline CuO are prepared by the treatment of Cu(NO₃)₂ and Pd(OAc)₂ in polyethylene glycol (PEG-6000). The shapes of the CuO/Pd composite are dependent on the amount of PEG used. Suzuki coupling was catalyzed efficiently by the oval-shaped material, whereas the rod shape facilitates the cyanation reaction. The CuO/Pd catalyst is recovered and reused for subsequent Suzuki reactions; however, cyanation poisons the catalyst for further use. Both these reactions are very clean and high yielding.     

PEG-400 as green reaction medium for Lewis acid-promoted cycloaddition reactions with isoeugenol and anethole

A simple and efficient one-pot method for the synthesis of new 2,4-diaryl-1,2,3,4-tetrahydroquinolines using a three-component imino Diels-Alder cycloaddition between trans-isoeugenol or trans-anethole, anilines, and benzaldehyde in the presence of BF₃·OEt₂ in PEG-400, a green and reusable solvent, has been developed. Also, BF₃·OEt₂-catalyzed formal [3+2] cycloaddition reaction of trans-isoeugenol or trans-anethole with 1,4-benzoquinone in PEG-400 to give dihydrobenzo[b]furan derivatives has been described.     

KF/Al2O3 and PEG-400 as a recyclable medium for the selective α-selenation of aldehydes and ketones. Preparation of potential antimicrobial agents

2-Phenylseleno aldehydes and ketones were selectively obtained using solid-supported catalyst (KF/Al₂O₃) and PEG-400 as clean, recyclable medium in good to excellent yields. The method was applied in the preparation of highly functionalized 2-phenylseleno citronellal and citronellol, potential bactericide agents. The catalytic system KF/Al₂O₃ and PEG-400 can be re-used for four times without previous treatment.     

A facile synthesis of novel benzofuran-2-yl(9-methyl-9H-carbazol-3-yl)methanones

A facile synthesis of hitherto unreported benzofuran-2-yl(9-methyl-9H-carbazol-3-yl)methanones (3a?Cl) is described. The synthesis mainly relies on the ultrasound-assisted Rap?CStoermer reaction of 3-chloroacetyl-9-methyl-9H-carbazole (1) with a variety of salicylaldehydes, as well as 2-hydroxy-1-naphthaldehyde (2) in CH₃CN, with the presence of PEG-400 as a catalyst. This procedure offers easy access to benzofuran-2-yl(carbazolyl)methanone derivatives in a short reaction time and the products are achieved in good yields.     

PEG-400 as an efficient and recyclable reaction medium for the synthesis of 2-aryl-2-methyl-4,5-diphenyl-2,3- dihydro-2H-imidazoles

A productive natural method has been produced for the synthesis of 2-aryl-2-methyl-4,5-diphenyl-2,3-dihydro-2H-imidazoles in great yields under catalyst free-conditions utilizing polyethylene glycol (PEG-400) as a green reaction medium. The highlights of this new method are shorter reaction times, good yields, room temperature, and use of nontoxic, inexpensive, and recyclable PEG-400.     

Microencapsulated Cu(acac)2: a recoverable and reusable polymer-supported copper catalyst for aziridination of olefins

Microencapsulated copper(II) acetylacetonate was prepared and used in the aziridination of alkenes employing [N-(p-tolylsulfonyl)imino]phenyliodinane (PhINTs) as the nitrogen source. Microencapsulated copper(II) acetylacetonate [MC-Cu(acac)₂] catalyst was reused for several cycles with consistent activity.