A Nitrogen,Sulfur co-Doped Porphyrin-based Covalent Organic Framework as an Efficient Catalyst for Oxygen Reduction

Oxygen reduction reaction(ORR) is a significant reaction for energy conversion systems(such as fuel cells, metal-air batteries, etc.). It is an urgent need to develop cheap, durable and highly-active catalysts for efficient ORR. Hence, we report a metal-free nitrogen and sulfur co-doped porphyrin-based covalent organic framework(COF) as a high-efficiency ORR catalyst[the onset potential(E_o) is 0.79 V and the half-wave potential(E_1/2) is 0.70 V]. The double doping of N and S atoms causes uneven charge distribution around carbon atoms, which can act as catalytic active centers, improving ORR activity. Compared with single-atom doping, double atoms doping exhibits a higher activity due to the synergistic effect between different elements. These results demonstrate that reasonable design of stable metal-free COFs with a high electrochemical activity can promote their wide applications.     

Mixed Linker Metal Organic Framework as an Efficient and Reusable Catalyst for Suzuki Miyaura Coupling Reaction

Series of metal organic frameworks from nitrogen based ligand were synthesized as efficient and reusable catalyst via mixed linker methods. The thermogravimetric study of the mixed linker metal organic framework (MIXMOF) reveals that the complexes are potential thermally stable materials. The palladium supported catalysts exhibits high catalytic activity toward the Suzuki-Miyaura cross coupling reaction and can be reused several times without any visible loss of activity even after five consecutive times.     

Silica Supported Methanesulfonic Acid as an Efficient and Reusable Heterogeneous Catalyst for the Synthesis of Amidoalkyl Naphthols

A green protocol for the preparation of amidoalkyl naphthols from three‐component one‐pot condensation of 2‐naphthol, aldehydes, amides or urea in the presence of silica supported methanesulfonic acid under thermal solvent‐free conditions has been described. The catalyst is stable, efficient, easily prepared, and reusable. The remarkable features of this methodology are short reaction time, excellent yields, simple experimental and work‐up procedures.     

Alumina Perchloric Acid (Al 2 O 3 -HClO 4 ) as an Efficient Heterogeneous Catalyst for Modified Preparation of Trimethylsilyl Ethers

A highly efficient and mild procedure for the trimethylsilylation of a wide variety of alcohols, including primary, benzylic, secondary, hindered secondary, tertiary, phenols, and oximes with hexamethyldisilazane (HMDS) using alumina perchloric acid (Al ₂ O ₃ -HClO ₄ ) as recyclable heterogeneous catalyst in excellent yields with short reaction times (3?65 min) under ambient conditions is described.     

A Porphyrin‐Based Porous rtl Metal–Organic Framework as an Efficient Catalyst for the Cycloaddition of CO2 to Epoxides

A porous rtl metal–organic framework (MOF) [Mn₅L(H₂O)₆?(DMA)₂]?5DMA?4C₂H₅OH ( 1? Mn) (H₁₀L=5,10,15,20‐tetra(4‐(3,5‐dicarboxylphenoxy)phenyl)porphyrin; DMA=N,N′‐dimethylacetamide) was synthesized by employing a new porphyrin‐based octacarboxylic acid ligand. 1? Mn exhibits high Mn^II density in the porous framework, providing it great Lewis‐acid heterogeneous catalytic capability for the cycloaddition of CO₂ with epoxides. Strikingly, 1? Mn features excellent catalytic activity to the cycloaddition of CO₂ to epoxides, with a remarkable initial turnover frequency 400 per mole of catalyst per hour at 20 atm. As‐synthesized 1? Mn also exhibits size selectivity to different epoxide substrates on account of their steric hindrance. The high catalytic activity, size selectivity, and stability toward the epoxides on catalytic cycloaddition of CO₂ make 1? Mn a promising heterogeneous catalyst for fixation and utilization of CO₂.     

Palladium Supported on Porous Organic Polymer as Heterogeneous and Recyclable Catalyst for Cross Coupling Reaction

Palladium immobilized on an amide and ether functionalized porous organic polymer (Pd@AEPOP) is reported to be an effective heterogeneous catalyst for the Heck cross-coupling reaction of aryl iodides with styrene for the synthesis of diphenylethene derivatives. Excellent yields can be obtained using a 0.8 mol% Pd catalyst loading under the optimized reaction condition. The heterogeneous Pd@AEPOP catalyst can also be applied on the Suzuki reaction and the reduction of nitroarene.     

硅胶硫酸:一种在温和及无溶剂条件下一锅法合成1,4-二氢吡啶的高效多相催化剂(英文)

A series of 1,4-dihydropyridines have been prepared by a one-pot condensation of aldehydes,ethyl acetoacetate,and ammonium acetate in the presence of a heterogeneous catalyst silica sulfuric acid at room temperature under solvent-free condition. This new protocol has the advantage of short reaction time and excellent yields,and is an environmentally benign route to the synthesis of 1,4-dihydropyridines.     

Trifluoroacetic Acid as an Efficient Catalyst for One-Pot,Four-Component Synthesis of 1,2,4,5-Tetrasubstituted Imidazoles Under Microwave-Assisted,Solvent-Free Conditions

An efficient method for synthesis of various tetrasubstituted imidazoles, using trifluoroacetic acid (TFA) as a catalytic support, by four-component condensation of benzil, aldehydes, amines, and ammonium acetate under microwave-irradiated, solvent-free conditions is described.     

A Pyridinium-Pyridinium Zinc(II) Porphyrin Ion Porous Organic Polymer as Efficient Heterogeneous Catalyst for Cycloaddition of Epoxides with CO2

A zinc(II)porphyrin-based ion porous organic polymer (ZnTPyPBr₄-iPOP) is successfully synthesized from newly designed pyridinium-functionalized cationic Zn-porphyrin monomer (ZnTPyPBr₄) by free radical self-polymerization, and is employed as an efficient bifunctional heterogeneous catalyst for CO₂ cycloaddition reaction with epoxides. The ZnTPyPBr₄-iPOP exhibits excellent catalytic performance and good substrate expansion in CO₂ cycloaddition reaction under solvent-free and cocatalyst-free conditions with a TOF as high as 15,500 h⁻¹ for the cycloaddition of CO₂ and epichlorohydrin. The synergistic effect of zinc(II)porphyrin as the Lewis acidic site and the Br⁻ anion as the nucleophile in ZnTPyPBr₄-iPOP responds to the high catalytic activity. Moreover, ZnTPyPBr₄-iPOP can easily be recovered and reused at least seven times without the loss of activity. This work provides a valuable approach for the synthesis of novel and efficient heterogeneous catalyst for CO₂ cycloaddition.     

碳化多孔有机骨架制备氮掺杂多孔碳及其气体吸附研究

通过简单的一步碳化方法, 以含氮的多孔有机骨架JUC-Z2为碳前驱物制备出氮掺杂多孔碳材料. 与原始JUC-Z2材料相比, 制备的多孔碳材料显示出明显提高的气体吸附量和增强的吸附焓. 其中JUC-Z2-900的CO₂吸附量高达113 cm³·g^-1, H₂吸附量也达到246 cm³·g^-1, 超过了大部分报道的多孔材料. 尤其是JUC-Z2-900的CH₄吸附量在273 K, 1 bar下高达60 cm³·g^-1, 据我们所知, 这一值为目前报道材料的最高值. 除此之外, 样品还显示出选择性吸附CO₂的能力, 273 K下, JUC-Z2-900的CO₂/N₂的选择性高达10, CO₂/H₂的选择性也高达66. 另外, 样品具有很高的热稳定性, 有望应用在碳捕获和清洁能源储存等领域.     

Efficient One-Pot Synthesis of Polyhydroquinoline Derivatives Using Silica Sulfuric Acid as a Heterogeneous and Reusable Catalyst Under Conventional Heating and Energy-Saving Microwave Irradiation

An efficient Hantzsch four-component condensation reaction for the synthesis of polyhydroquinoline derivatives was reported under two conditions: solvent-free conventional heating and energy-saving microwave irradiation. The process is simple and environmentally benign, and the use of a heterogeneous and reusable catalyst, high yields, and short reaction times are the key features of this protocol.     

Carbon-Based Solid Acid as An Efficient and Reusable Catalyst for One-Pot Synthesis of Tetrasubstituted Imidazoles under Solvent-Free Conditions

Carbon‐based solid acid catalyst was found to be highly efficient, eco‐friendly and recyclable heterogeneous catalyst for the multicomponent reaction of benzil, aromatic aldehyde, primary amine and ammonium acetate, giving rise to 1,2,4,5‐tetrasubstituted imidazoles in good to excellent yields. The present methodology offers several advantages, such as high yields, short reaction time, mild reaction condition and a recyclable catalyst with a very easy work up.     

Silica Sulfuric Acid: An Efficient,Reusable, Heterogeneous Catalyst for the One-Pot,Five-Component Synthesis of Highly Functionalized Piperidine Derivatives

A series of highly functionalized piperidine derivatives was synthesized through one-pot, five-component reaction of aldehydes, amines, and β-ketoesters. Silica sulfuric acid efficiently catalyzes the reaction to afford the corresponding piperidine derivatives in good yields. As a representative example, heating of 4-methylaninle, 4-fluorobezaldehyde, and methyl-acetoacetate in methanol in the presence of silica sulfuric acid furnished the corresponding ethyl 2,6-bis(4-fluorophenyl)-1-p-tolyl-4-(p-tolylamino)-1,2,5,6-tetrahydropyridine-3-carboxylate in excellent yield (85%). Most of the synthesized compounds were screened in vitro for their antibacterial and antifungal activities. Most of compounds showed significant antibacterial activity.     

Alumina Sulfuric Acid as an Efficient and Recyclable Heterogeneous Catalyst for the O-Silylation of Alcohols,Phenols, and Oximes

Alumina sulfuric acid as a recyclable catalyst conducts the transformation of various types of alcohol, phenols, and oximes with hexamethyldisilazane (HMDS) to the corresponding O-trimethylsilylated compounds in good to excellent yields under mild and ambient conditions with short reaction times. The method is highly selective for the conversion of primary alcohols in the presence of secondary and tertiary alcohols. Additionally, the catalyst can be easily recovered and reused at least eight times without detectable loss of reactivity.     

A Polyoxometalate‐Encapsulating Cationic Metal–Organic Framework as a Heterogeneous Catalyst for Desulfurization

A new cationic triazole‐based metal–organic framework encapsulating Keggin‐type polyoxometalates, with the molecular formula [Co(BBPTZ)₃][HPMo₁₂O₄₀]?24 H₂O [compound 1 ; BBPTZ=4,4′‐bis(1,2,4‐triazol‐1‐ylmethyl)biphenyl] is hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. The structure of compound 1 contains a non‐interpenetrated 3D CdSO₄ (cds)‐type framework with two types of channels that are interconnected with each other; straight channels that are occupied by the Keggin‐type POM anions, and wavelike channels that contain lattice water molecules. The catalytic activity of compound 1 in the oxidative desulfurization reaction indicates that it is not only an effective and size‐selective heterogeneous catalyst, but it also exhibits distinct structural stability in the catalytic reaction system.     

SiO2-NaHSO4 as an Efficient Reusable Heterogeneous Catalyst for the One-Pot Three-Component Synthesis of Octahydro-quinazolin-2,5-diones in Water

An environmentally benign method for the synthesis of octahydro-quinazolin-2,5-diones by the reaction of aromatic aldehydes,dimedone,and urea in the presence of SiO2-NaHSO4 is reported.SiO2-NaHSO4 acts...     

COF固载铜盐催化苯硼酸与咪唑的Chan-Lam偶联反应

制备了一种含有联吡啶位点的共价有机骨架(COF)材料TpBpy,并通过配体上的联吡啶位点固载铜盐实现了功能化,得到的Cu@TpBpy具有大量的不饱和铜配位位点和高表面积,可用作苯硼酸与咪唑的Chan-Lam偶联反应的多相催化剂.通过优化溶剂、铜源、碱及反应时间等反应条件,发现使用质子极性溶剂MeOH时的反应产率最高,而Cu(OAc)₂@Tp Bpy是效果最佳的催化剂,可溶性有机碱三乙胺(TEA)的促进效果最好.Cu(OAc)₂@TpBpy在碱TEA的促进下于70℃催化咪唑与苯硼酸反应4 h后,得到目标产物1-苯基咪唑的最大产率为66%.在最优反应条件下进行了底物拓展,结果表明,取代基的位阻效应对催化体系影响显著,其中对位取代基的4-氯苯硼酸的产率最高(62%).     

氨基磺酸催化剂在有机合成中的应用

综述了近年来氨基磺酸作为一种绿色催化剂在有机合成中的应用,主要包括酯化与酯交换、基团保护、氮杂Diels-Alder、重排、取代及缩合等反应。参考文献58篇。     

Bioglycerol-Based Sulfonic Acid-Functionalized Carbon Catalyst as an Efficient and Reusable Catalyst for One-Pot Synthesis of 3- Substituted-2H-1,4-Benzothiazines

Abstract

A simple and efficient synthetic protocol has been developed for the synthesis of 3-substituted-2H-1,4-benzothiazines by using bioglycerol-based sulfonic acid-functionalized carbon catalyst, devoid of corrosive acidic and basic reagents. The developed method has the advantages of good to excellent yields, short reaction times, operational simplicity, and a recyclable catalyst.     

Highly Active La(III)-Based Metal-Organic Framework as a Heterogeneous Lewis Acid Catalyst for Friedel-Crafts Alkylation

In this study, a novel La(III)-based two-dimensional (2D) metal-organic framework, [La_2/3(qptca)_1/2] (referred to as SLX-2), from LaCl₃ and 1,1′ : 4′,1′′ : 4′′,1′′′ : 4′′′,1′′′′-quinquephenyl]-2,2′′,2′′′′,5′′-tetracarboxylic acid (H₄qptca) was synthesized by conventional solvothermal method and thoroughly characterized by using X-ray single-crystal diffraction, powder X-ray diffraction, and thermogravimetric analyses. The 2D SLX-2 features a unique lanthanum center exposed to the skeleton and was used as an efficient Lewis acid catalyst for the Friedel-Crafts alkylation of indole and pyrrole with β-nitrostyrene along with a wide substrate scope, giving the desired products in good-to-high yields under the optimal reaction conditions. Furthermore, the catalyst was used for twenty cycles, with nearly no effect on its activity, and the reaction was heterogeneous in nature. Moreover, compared to the previous hydrogen-bond-donating MOF catalysts for such alkylation reactions, SLX-2 showed an excellent stability toward harsh acidic and basic environment, and gave comparable catalytic activities.