一种经MCM-41负载双齿膦钯(0)配合物催化的羰基化Suzuki偶联合成二芳酮的新途径

在催化量的MCM-41负载双齿膦钯(0)配合物存在下,芳基碘化物和芳基硼酸、一氧化碳在常压下能顺利进行羰基化Suzuki偶联反应,高产率地生成了各种二芳酮化合物。MCM-41负载双齿膦钯(0)配合物具有比PdCl2(PPh3)2 更高的活性和选择性,且可回收再用10次其活性基本不变,为各种功能化二芳酮的合成提供了方便实用的新途径。     

Asymmetric Transfer Hydrogenation Catalyzed by Mesoporous MCM‐41‐Supported Chiral Ru‐Complex

Chiral N‐sulfonyldiamine was successfully anchored on mesoporous MCM‐41 silica. The MCM‐41‐supported chiral N‐sulfonyldiamine was used as an efficient heterogeneous chiral ligand in the asymmetric transfer hydrogenation of ketones. This heterogeneous system offered satisfactory enantioselectivities up to 94 % with excellent conversions.     

Palladium chloride anchored on organic functionalized MCM‐41 as a catalyst for the Heck reaction

Palladium chloride was grafted to amino‐functionalized MCM‐41 to prepare heterogeneous catalysts. XRD, N₂ adsorption–desorption isotherms, IR, ¹³C and ²⁹Si cross‐polarization magic‐angle spinning NMR spectroscopy and XPS techniques were employed to characterize the catalytic materials. The heterogeneous palladium catalyst exhibited excellent catalytic activity for the Heck vinylation of iodobenzene with methyl acrylate, giving 92% yield of methyl cinnamate in the presence of N‐methylpyrrolidone (NMP) and triethylamine (Et₃N). The stability of the heterogeneous catalyst was also studied in detail. The catalytic tests showed that the palladium leaching correlated to solvent, base and palladium loading. The heterogeneous catalyst exhibited excellent stability towards loss of activity and palladium leaching was not observed during six recycles in the presence of toluene and Na₂CO₃. Copyright © 2007 John Wiley & Sons, Ltd.     

A phosphine‐free heterogeneous Suzuki–Miyaura reaction of aryl bromides catalyzed by MCM‐41‐supported tridentate nitrogen palladium complex under air

MCM‐41‐supported tridentate nitrogen palladium(II) complex [MCM‐41‐3 N‐Pd(II)] was conveniently synthesized from commercially available and cheap 3‐(2‐aminoethylamino)propyltrimethoxysilane via immobilization on MCM‐41, followed by reacting with pyridine‐2‐carboxaldehyde and PdCl₂. It was found that this palladium complex is an excellent catalyst for the Suzuki–Miyaura coupling reaction of aryl bromides on two points: (i) the use of 5 × 10⁻⁴ mol equiv. of MCM‐41‐3 N‐Pd(II) under air afforded the coupling products efficiently after easy workup; (2) the catalyst can be reused many times without loss of catalytic activity. Copyright © 2011 John Wiley & Sons, Ltd.     

Mesoporous Silica MCM‐41 Supported N‐Heterocyclic Carbene‐Pd Complex for Heck and Sonogashira Coupling Reactions

Heterocyclic carbene‐Pd complex was anchored onto the mesoporous silica MCM‐41 which exhibits high catalytic activity in Heck reaction under phosphine free reaction conditions for the reaction of iodo/bromoarenes with olefinic compounds such as butyl acrylate, isopropyl acrylate and styrene. This catalytic system also showed high activity for Sonogashira coupling reaction of various aryl halides under copper, phosphine and solvent‐free reaction conditions. The air and thermally stable catalyst were reused several times without significant loss of its activity. High efficiency of the catalyst along with its recycling ability and the rather low Pd‐loading demonstrated in both Heck and Sonogashira coupling reactions are the merits of the presented catalyst system.     

固载液相铂催化剂催化3-氯丙烯硅氢加成反应

固载液相铂催化剂催化3-氯丙烯硅氢加成反应;固载液相铂催化剂;硅氢加成;催化;氯丙烯     

Mesoporous Molecular Sieve MCM‐41 as a Novel and Efficient Catalyst to Synthesis of 2‐Substituted Benzimidazoles

o‐Phenylenediamine derivatives readily react with benzoyl chloride derivatives in the presence of MCM‐41 as catalyst to yield 2‐substituted benzimidazoles in very good yields.     

MCM‐41‐Immobilized [Rh(cod)OCH3]2 Complex – A Hybrid Catalyst for the Polymerization of Phenylacetylene and Its Ring‐Substituted Derivatives

The immobilization of [Rh(cod)OCH₃]₂ (cod = cycloocta‐1,5‐diene) on mesoporous molecular sieves MCM‐41 provides the first inorganic‐type hybrid catalyst, which affords heterogeneous polymerization of phenylacetylene and its ring‐substituted derivatives, – 2‐fluorophenylacetylene, 4‐fluorophenylacetylene, and 4‐pentylphenylacetylene – into readily isolable high‐molecular‐weight (M̄_w from 50 000 to 180 000) substituted polyvinylenes of high cis‐transoid structure. The activity of this catalyst is compared with that of homogeneous catalyst [Rh(cod)OCH₃]₂.     

A novel heterogeneous nanocatalyst: 2‐Methoxy‐1‐phenylethanone functionalized MCM‐41 supported Cu(II) complex for C‐S coupling of aryl halides with thiourea

An environmentally friendly copper‐based catalyst supported on 2‐Methoxy‐1‐phenylethanone functionalized MCM‐41 was prepared and characterized by FT‐IR, FE‐SEM, TEM, XRD, EDX, BET and ICP techniques. The catalyst was applied for the C?S cross‐coupling reaction of aryl halides with thiourea. Corresponding products were produced in good yields in aerobic conditions. The catalyst could be recovered and recycled for several times.     

MCM‐41 Supported Aminopropylsiloxane Palladium Acetate Complex: A Highly Active and Stereoselective Catalyst for Heck Reaction

A new MCM‐41 supported aminopropylsiloxane palladium acetate was prepared and characterized. This catalyst is highly active and stereoselective for Heck reaction at 70°C.     

MCM‐41‐SO3H as a Highly Efficient Sulfonic Acid Nanoreactor for the Rapid and Green Synthesis of Some Novel Highly Substituted Imidazoles under Solvent‐Free Condition

Nanosized MCM‐41‐SO₃H based on ordered mesoporous silica material with a covalent sulfonic acid group was synthesized and used as acid catalyst for the new, simple, convenient and green synthesis of 2,4,5‐trisubstituted and 1,2,4,5‐tetra‐substituted imidazoles. Also some of synthesis products are new. Echo‐friendly protocol, short reaction times, easy and quick isolation of the products and excellent yields are the main advantages of this procedure.     

Copper(I)‐N2S2‐salen type complex covalently anchored onto MCM‐41 silica: an efficient and reusable catalyst for the A3‐coupling reaction toward propargylamines

The immobilization of copper complexes by covalent anchoring of the ligand on the surface of mesoporous MCM‐41 has been described. Bis[2‐(phenylthio)benzylidene]‐1,2‐ethylenediamine as a new N₂S₂ donor salen‐type ligand was covalently anchored onto nanopores of MCM‐41 coordinated with copper (I) halide. The organic–inorganic hybrid material was achieved readily using 3‐mercaptopropyltrimethoxysilane as a reactive surface modifier. 2‐Nitrobenzaldehyde was reacted smoothly with the thiol moieties in order to form functionalized nanoporous silica with carbaldehyde groups. The resulting supported organic moieties were converted to thiosalen ligand and coordinated with CuX (X = CN, Cl, Br, I). Characterization of the heterogeneous catalyst by X‐ray diffraction, N₂ sorption, FT‐IR, diffuse reflectance UV‐visible and TGA techniques indicated successful grafting of the copper complex inside the nano‐channels of MCM‐41. The heterogenized catalyst was evaluated by the Mannich condensation reaction of aldehydes, amines and alkynes. In this reaction, the corresponding propargylamines were obtained as single products in good to excellent yields. Factors such as reaction temperature, solvent, catalyst loading, leaching and reusability of the catalyst also were discussed. The use of MCM‐41 as support permits an easier separation and recycles with only a marginal decrease in reactivity. Copyright © 2013 John Wiley & Sons, Ltd.     

Removal of Copper‐phthalocyanine from Aqueous Solution by Cationically Templated MCM‐41 and MCM‐48 Nanoporous Adsorbents

The effect of cationic template on the adsorption of copper-phthalocyanine-3,4’,4",4"’-tetrasulfonic acid tetra-     

MCM‐41‐supported mercapto palladium(0) complex: an efficient and recyclable catalyst for the heterogeneous Stille coupling reaction

The Stille cross‐coupling reaction of organostannanes with aryl halides was achieved in the presence of a catalytic amount of MCM‐41‐supported mercapto palladium(0) complex (1 mol%) in DMF? H₂O (9:1) under air atmosphere in good to high yields. This MCM‐41‐supported palladium catalyst can be reused at least 10 times without any decrease in activity. Copyright © 2009 John Wiley & Sons, Ltd.     

Phthalhydrazide immobilized on MCM‐41 as a potent and recoverable catalyst for the synthesis of pyrrolo[2,1‐a]isoquinolines

We present a study on the synthesis, characterization, and application of phthalhydrazide‐functionalized MCM‐41 (P‐MCM‐41) as a novel and efficient heterogeneous basic catalyst. The described catalyst was fully characterized via various techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X‐ray (EDX), X‐ray diffraction (XRD), and Fourier transform infrared (FT‐IR). P‐MCM‐41 efficiently catalyzed the four‐component reaction of arylaldehydes, Meldrum's acid, alkyl isocyanides, and isoquinoline in CHCl₃ to prepare pyrrolo[2,1‐a]isoquinolines in good yields.     

Tubular Morphology of Mesoporous Silica MCM‐41

We investigated detailed conditions for synthesizing the tubular form of MCM‐41 mesoporous aluminosilicate. The method is the delayed neutralization method in which the rate of neutralization is one of the controlling factors. Rapid neutralization results in the particulate form while gradual neutralization leads to tubules. It is found that the tubule morphology has several sub‐categories. There are thick‐walled, think‐walled hollow tubular MCM‐41 and solid core tubules. There are void structures in the channel framework that makes the nanochannels to be effectively interconnected.     

Synthesis,Characterization and Catalysis of Ce‐MCM‐41

The cerium‐containing MCM‐41 (Ce‐MCM‐41) has been synthesized by direct hydrothermal method. The low‐angle XRD patterns revealed the typical five major peaks of MCM‐41 type hexagonal structures. The interplanar spacing d₁₀₀ = 38.4 Å was obtained that can be indexed on a hexagonal unit cell parameter with a_o = 44.3 Å which was larger than that of pure siliceous MCM‐41 (Si‐MCM‐41). Transmission electron micrograph shows the regular hexagonal array of uniform channel characteristics of MCM‐41. The BET surface area of Ce‐MCM‐41 was 840 m²/g, which is much reduced as compared to that of Si‐MCM‐41, with the pore size of 26.9 Å and mesopore volume of 0.78 cm³/g were measured by nitrogen adsorption‐desorption isotherm at 77 K. Along with the results, the synthesized Ce‐MCM‐41 exhibited a well‐ordered MCM‐41‐type mesoporous structure with the incorporation of cerium. Using Ce‐MCM‐41 as a support, the Rh (0.5 wt%) catalyst exhibited very high activity for the NO/CO reactions.