A highly chemoselective Boc protection of amines using sulfonic-acid-functionalized silica as an efficient heterogeneous recyclable catalyst

A facile and versatile method for the chemoselective Boc protection of amines has been developed by a treatment with (Boc)₂O in the presence of sulfonic-acid-functionalized silica as a catalyst. The method is general for the preparation of N-Boc derivatives of aliphatic (acyclic and cyclic), aromatic, and heteroaromatic amines; primary and secondary amines; aminols, amino-esters; and sulfonamides. The catalyst works under heterogeneous conditions and can be recycled.     

Modulated large-pore mesoporous silica as an efficient base catalyst for the Henry reaction

In this study, mesoporous silica materials with tuned pores and surface areas were successfully synthesized by adjusting the amount of applied hexane and controlling the hydrothermal temperature. The synthesized silica materials were then functionalized by an amine group to produce solid base catalysts and be applicable as efficient heterogeneous base catalysts for the Henry reaction. The mesoporous silica catalysts possessing large-pores and surface area expose their active catalytic sites and thereby improve contacts with reactants fulfilling the reactions expeditiously in comparison with solid base catalysts possessing small-pores and surface area. The results indicated that the yield of the products is significantly dependent on the structure of the applied solid base catalysts. The modulated large-pore solid base catalysts presented high catalytic activity in Henry reactions and could be reused for five consecutive cycles.     

Nickel(II) chloride as an efficient and useful catalyst for chemoselective thioacetalization of aldehydes

A wide variety of acyclic and cyclic dithioacetals can be prepared chemoselectively from the corresponding aldehydes by employing a catalytic amount of nickel(II) chloride in dry CH₂Cl₂-MeOH (5:1) at room temperature in good yields. Some of the major advantages of this procedure are high chemoselectivity, ease of operation, high yields and also compatibility with other protecting groups.     

Ferrous methanesulfonate as an efficient and recyclable catalyst for chemoselective synthesis of 1,1-diacetate from aldehydes

Ferrous methanesulfonate catalysing the conversion of aromatic,heteroaromatic,unsaturated,and aliphatic aldehydes to 1,1- diacetates at room temperature under solvent-free condition has been developed.The catalytic activity of seventeen metal methanesulfonates was compared under the same condition,ferrous methanesufonate proved to be the best.It can be easily recovered and reused for several times without distinct deterioration in catalytic activity.During the competitive protection between a ketone and ...     

Cobalt nanoparticles supported on ionic liquid‐functionalized multiwall carbon nanotubes as an efficient and recyclable catalyst for Heck reaction

A novel and environmentally friendly cobalt nanoparticle catalyst supported on ionic liquid‐functionalized multiwall carbon nanotubes was successfully prepared and evaluated as a heterogeneous catalyst for the Mizoroki–Heck reaction. Several reaction parameters, including type and amount of solvent and base, were evaluated. This nanocatalyst could also be recovered and reused at least six times without any discernible decrease in its catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Solid supported Pd(0): an efficient recyclable heterogeneous catalyst for chemoselective reduction of nitroarenes

Solid supported palladium(0) (SS-Pd) catalyzed highly chemoselective reduction of nitroarenes to the corresponding anilines was accomplished under a milder reaction condition. This catalyst showed high compatibility with various reducing agents (NaBH₄, Et₃SiH, and NH₂NH₂·H₂O) and a large number of reducible functional groups such as sulfonamide, amides, carboxylic acid, ester, alcohol, halide, hetero cycle, nitrile, alkene, carbonyl, O-benzyl, and N-benzyl were tolerated. Most of the reactions were clean and high yielding. The SS-Pd catalyst could be recycled up to seven runs without significant loss of activity.     

A high loading sulfonic acid-functionalized ordered nanoporous silica as an efficient and recyclable catalyst for chemoselective deprotection of tert-butyldimethylsilyl ethers

A high loading sulfonic acid-functionalized ordered nanoporous silica efficiently catalyzes the deprotection of a variety of alcoholic TBDMS (tert-butyldimethylsilyl)ethers in methanol. The catalyst shows high thermal stability (up to 240 °C) and can be recovered and reused for at least seven reaction cycles without loss of reactivity. This method can be used to deprotect TBDMS ethers of alcohols in the presence of TBDMS ethers of phenols.     

Tetrabutylammonium tribromide (TBATB) as an efficient generator of HBr for an efficient chemoselective reagent for acetalization of carbonyl compounds

Acyclic and cyclic acetals of various carbonyl compounds were obtained in excellent yields under a mild reaction condition in the presence of trialkyl orthoformate and a catalytic amount of tetrabutylammonium tribromide (TBATB) in absolute alcohol. Chemoselective acetalization of an aldehyde in the presence of ketone, unsymmetrical acetal formation, shorter reaction times, mild reaction conditions, the stability of acid-sensitive protecting groups, high efficiencies, facile isolation of the desired products, and the catalytic nature of the reagent make the present methodology a practical alternative.     

Bis-chelate tetracarbene palladium(II) complex as an efficient and recyclable catalyst precursor for Heck reaction

A homoleptic Pd(II) complex with two chelating di-N-heterocyclic carbene (NHC) ligands has been synthesized and its square planar molecular geometry has been determined by X-ray diffraction analysis. The complex proved to be an efficient catalyst having exceedingly high turnover number and good reusability in Heck reaction.     

A highly efficient and reusable mesoporous supported Co(II) catalyst for chemoselective deprotection of aryl acetates

Chemoselective deprotection of aryl acetates is successfully carried out in excellent yield using a mesoporous silica-supported (Salen) Co(II) catalyst. The catalyst shows high thermal stability and also can be recovered and reused at least 10 times without any significant loss of its catalytic activity. The present process is environmentally benign and economical.     

Dialkylaminopyridine-functionalized mesoporous silica nanosphere as an efficient and highly stable heterogeneous nucleophilic catalyst

A new nucleophilic catalytic system comprised of dialkylaminopyridine-functionalized mesoporous silica nanosphere (DMAP-MSN) has been synthesized and characterized. We have demonstrated that this material is an efficient heterogeneous catalyst for Baylis-Hillman, acylation, and silylation reactions with good reactivity, product selectivity, and recyclability. We envision that this DMAP-functionalized mesoporous silica material can also serve as an effective heterogeneous catalyst for many other catalytic nucleophilic reactions.     

碳-硅复合介孔磺酸催化剂的制备及其在缩醛(酮)反应中的应用

采用浸渍法将糠醇负载在铝改性的SBA-15介孔孔道中,经550℃不完全碳化制备了结构规整、含多苯环的中空管状硅碳复合介孔材料.结果表明,通过温和磺酸化作用可使磺酸基团成功取代在多苯环上,其酸量随着多苯环涂层厚度变化在0.38~0.84 mmol/g范围内可控调变.相比于蔗糖作为糖源的复合固体酸,所制碳多苯环-硅酸催化剂具有中空碳纳米管堆积的类似CMK-5介孔结构,以及较大的反应空间、稳定的机械性能、较高的比表面和大量可以接触的质子酸中心,因而在大分子缩醛(酮)反应中表现了良好的催化性能.     

Sulfonic acid functionalized silica as an efficient heterogeneous recyclable catalyst for one‐pot synthesis of 2‐substituted benziimidazoles

An efficient one‐pot synthesis of 2‐substituted benzimidazoles from o‐phenylenediamine and aldehydes in the presence of sulfonic acid functionalized silica at room temperature is reported.     

Synthesis of bis(indolyl)methanes using silica gel as an efficient and recyclable surface

Here we describe a simple, clean, and efficient solvent-free protocol for the synthesis of bis(indolyl)methanes promoted by silica gel. The products were obtained in good to excellent yields through the reaction of indoles with cyclohexanone and a range of aldehydes. The silica gel was easily recovered and utilized for further reactions without loss of activity.     

Zinc(II) complex immobilized on amine functionalized silica gel: a novel,highly efficient and recyclable catalyst for multicomponent click synthesis of 1,4-disubstituted 1,2,3-triazoles

We report a highly efficient and recyclable heterogeneous zinc catalytic system via covalent immobilization of 2-hydroxyacetophenone (2-HAP) onto an amine functionalized silica gel followed by metallation with zinc chloride and its catalytic application in three component click synthesis of 1,4-disubstituted 1,2,3-triazoles. The structure of the synthesized organic–inorganic hybrid material (SiO₂@APTES@2HAP-Zn) has been confirmed by various physicochemical characterization techniques, such as solid-state ¹³C CPMAS NMR spectroscopy, Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction analysis (XRD), Brunauer–Emmett–Teller (BET) surface area analysis, scanning electron microscopy (SEM), atomic absorption spectroscopy (AAS), energy-dispersive X-ray fluorescence spectroscopy (ED-XRF), and elemental analysis. The newly designed catalyst works under mild reaction conditions and also exhibits excellent performance in terms of good product yield and high turnover number (TON). One of the most important attributes of the present methodology is that the catalyst can be recycled several times without appreciable loss in its activity as proved by FTIR spectroscopy and SEM analysis. Besides, the heterogeneity test also confirms that no leaching of active catalytic species occurs from the silica supported zinc catalyst which confirms its remarkable structural stability under the reaction conditions.     

Nicotinic acid functionalized organomodified silica as an efficient heterogeneous catalyst for the synthesis of benzoyl fumarate

A new hybrid catalyst has been developed by incorporating nicotinic acid onto an organomodified silica. The catalyst was applied as a heterogeneous catalyst for the synthesis of benzoyl fumarate. The reactions work well in the presence of 20 wt % of the catalyst at room temperature to produce the desired products in high yield. The catalyst could be recovered and reused without appreciable change in activity.     

Sulfonic acid functionalized mesoporous MCM-41 silica as a convenient catalyst for Bisphenol-A synthesis

Sulfonic acid groups anchored to the surface of mesoporous MCM-41 silica have been identified with S K-edge XANES spectra and the material is an efficient catalyst for the liquid phase condensation of phenol with acetone to form Bisphenol-A with high selectivity.     

Construction of polymeric Cu(I) N-heterocyclic carbene complex utilizing terpyridine-Fe(II) as linkers: formation of an efficient and recyclable catalyst

A metal-coordination-driven self-assembly using the predesigned building block has been developed. Herein, the catalytic active NHC–Cu(I) units were introduced into the terpyridine metal coordination polymers. The self-assembled architecture, as a heterogeneous catalyst, was successfully used to catalyze the A³-coupling reaction of aldehyde, alkyne, and amine and Huisgen 1,3-dipolar cycloaddition reaction of azide and alkyne in high yields.     

The high-pressure liquid chromatographic separation of copper(II) and nickel(II) schiff base chelates on microparticulate silica

The separation of neutral copper and nickel chelates of two representative Schiff base ligands, N,N'-ethylenebis(acetylacetoneimine) and N,N'-ethylene-bis(salicylaldimine) is reported on a column of 10-μm diameter silica. Both pairs of chelates are well resolved with good peak shape and efficiencies when the mobile phase is 4 : 1 methylene chloride—acetonitrile. The u.v. detector response at 254 nm is linear over approximately three orders of magnitude of quantity of chelate injected; the detection limits are in the low nanogram range. Qualitative and quantitative elution of undegraded chelates was demonstrated by u.v. spectrophotometry, mass spectrometry and electron spin resonance spectroscopy.     

Cobalt(II)chloride catalyzed chemoselective thioacetalization of aldehydes

A mild and chemoselective dithioacetalization procedure for the protection of various aldehydes in the presence of catalytic amount of cobalt(II)chloride is described.