Synthesis of Fischer indole derivatives using carboxyl-functionalized ionic liquid as an efficient and recyclable catalyst

Fischer indole cyclization of phenylhydrazine and various ketones using carboxyl-functionalized ionic liquid, 1-carboxymethyl-3-methylimidazolium tetrafluoroborate (abbreviated as [cmmim][BF4]) as catalyst was successfully performed. The yields of thetarget compounds were 80-92%, the purities were 96-98%. The catalyst could be rocovered and reused for at least six times without significant loss in activity.     

Thermodynamically- and kinetically-controlled Friedel-Crafts alkenylation of arenes with alkynes using an acidic fluoroantimonate(v) ionic liquid as catalyst

By employing superacidic fluoroantimonate ionic liquid (IL), [bmim][Sb(2)F(11)], as catalyst, not only thermodynamically-controlled but also kinetically-controlled Friedel-Crafts alkenylations of arenes with alkynes have been realized for the first time.     

Supported ionic liquid catalyst (Pd-SILC) for highly efficient and recyclable Suzuki-Miyaura reaction

Highly efficient Suzuki-Miyaura coupling of aryl halides with arylboronic acid was realized in 50% aqueous ethanol at room temperature employing Pd(OAc)(2) immobilized in diethylaminopropylated (NDEAP) alumina pores with the aid of [bmim]PF(6), which enabled recycle use up to five times in 95% average yield and turnover number of two million.     

Efficient Heck reactions catalyzed by a highly recyclable palladium(II) complex of a pyridyl-functionalized imidazolium-based ionic liquid

The reactions of 2-(2-pyridyl)imidazole with alkyl iodides at 25 degrees C in the presence of base gave rise to 1-alkyl-2-(2-pyridyl)imidazole. Subsequent neat reactions with alkyl or polyfluoroalkyl halides at 100 degrees C, followed by anion exchange with LiN(SO(2)CF(3))(2), generated the mono-quaternary ionic liquids. All of them have excellent thermal stability and wide liquid range. Most of the salts with asymmetric N-substituents are liquid at room temperature. The effect of N-substituent variation and symmetry on NMR, TGA and DSC is discussed. Reaction of with palladium(II) chloride produced a mononuclear palladium ionic liquid complex, the structure of which was confirmed by single-crystal X-ray diffraction analysis. The Heck cross-coupling reactions using in ionic liquid demonstrated excellent stability and recyclability.     

Synthesis of triazoles from nonactivated terminal alkynes via the three-component coupling reaction using a Pd(0)-Cu(I) bimetallic catalyst

The synthesis of triazoles via the three-component coupling reaction of unactivated terminal alkynes, allyl carbonate, and trimethylsiyl azide under the Pd(0)-Cu(I) bimetallic catalyst is developed. The reaction most probably proceeds through the formation of a pi-allylpalladium azide complex and a copper-acetylide followed by a successive [3 + 2] cycloaddition. The deallylation of the resulting allyltriazoles proceeds very easily by the Ru-catalyzed isomerization followed by the ozonolysis of the resulting propenyltriazoles to give the triazoles in high yields.     

An imidazolium tosylate salt as efficient and recyclable catalyst for acetylation in an ionic liquid

A novel non-metallic salt, 1-butyl-3-methylimidazolium tosylate ([bmim][OTs]) dissolved in the ambient temperature ionic liquid of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), was found to be the efficient catalyst for acetylation with the advantages of good recyclability, avoidance of metal contamination, mild reaction conditions, and wide availability for substrates (alcohols, phenols, and amines), could completely replace organic bases, metal Lewis acids, or metallic triflates to fulfill acetylation by a nucleophilic catalytic mechanism, which was supported by ¹³C NMR analysis. Correspondence: Ye Liu, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Chemistry Department of East China Normal University, Shanghai 200062, China.     

A smart palladium catalyst in ionic liquid for tandem processes

New catalytic systems based on in situ and preformed palladium nanoparticles in ionic liquids (characterised by TEM) starting from palladium acetate or dipalladiumtris(dibenzylideneacetone) have been applied in the synthesis of 4-phenylbutan-2-one (II), a model compound for the preparation of fragrances. Imidazolium-based ionic liquid containing a methyl hydrogenophosphonate anion leads to an efficient Pd-catalyzed tandem coupling/reduction process, taking advantage of the multi-role of this solvent (nanoparticles stabiliser, base, hydrogen transfer agent). The influence of the mono-phosphine ligands (1-3) on the catalyst has been evaluated, showing that the ligand-free palladium system turns into the most appropriate for the formation of II using Pd(OAc)(2) as precursor. Fine-tuning conditions involved in this multi-parameter process have led us to propose a plausible mechanism based on the hydrogen transfer coming from the methyl hydrogenophosphonate anion.     

Novel method for catalyst immobilization using an ionic polymer: a case study using recyclable ytterbium triflate

A series of ionic polymers prepared by quarternization of cross-linked poly(4-vinylpyridine/styrene) (P/S) resins with several alkylating agents, including short-length PEG mesylate were used as polymeric supports to immobilize Yb(OTf)₃. The efficacy of the polymer-bound catalyst was examined in a Mannich-type reaction.     

A highly regioselective hydrophosphination of terminal alkynes with tetraphenyldiphosphine in the presence of palladium catalyst

A novel palladium-catalyzed hydrophosphination of alkynes with tetraphenyldiphosphine takes place regioselectively to provide vinylic phosphines, which undergo air-oxidation during workups, affording the corresponding vinylphosphine oxides in good yields.     

Hydrogenation of alkynes with a palladium anchored polystyrene catalyst

Treating chloromethylated polystyrene beads with anthranilic acid and then palladium chloride gives a material capable of catalyzing the cis-hydrogenation of alkynes. Hydrogenation of phenylacetylene (10mmol) with 0.017 g-atom (based on Pd) of catalyst at room temperature and 30 psig for 7.3 h resulted in 82 % styrene and 14% ethylbenzene. Methylphenylacetylene was converted to cis-1-phenylpropene (60%) and n-propylbenzene (17 %). Several other alkynes were also converted to cis alkenes. The catalyst is less selective than the Lindlar catalyst, but is air stable and stores well.     

Osmium tetroxide-(QN)2PHAL in an ionic liquid: a highly efficient and recyclable catalyst system for asymmetric dihydroxylation of olefins

In Os-catalysed asymmetric dihydroxylation using NMO as a co-oxidant, the combination of an ionic liquid and the new bis-cinchona alkaloid 2 generated in situ from (QN)2PHAL during reaction provided a simple and practical approach to the recycling of both catalytic components (osmium tetraoxide and chiral ligand).     

An ionic liquid-coordinated palladium complex: a highly efficient and recyclable catalyst for the Heck reaction

[structure: see text] The monoquaternary product of 2,2'-biimidazole with iodobutane is an ionic liquid that acts as both the solvent and ligand for catalytic reactions. A new palladium complex was prepared by adding PdCl(2) to this ionic liquid to form a catalytic solution that is effective for Heck reactions with good recyclability.     

Amine- and phosphine-free palladium(II)-catalyzed homocoupling reaction of terminal alkynes

An efficient, amine- and phosphine-free palladium(II)-catalyzed homocoupling of terminal alkynes has been developed. In the presence of PdCl₂, CuI, Me₃NO, and NaOAc, homocoupling of various terminal alkynes underwent smoothly to afford the corresponding diynes in moderate to high yields without any phosphine ligands. In contrast, the presence of a phosphine ligand (PPh₃) disfavored this palladium-catalyzed homocoupling procedure. Bases, solvents, and CuI have fundamental influence on the palladium-catalyzed homocoupling of terminal alkynes.     

A recyclable catalyst for asymmetric transfer hydrogenation with a formic acid-triethylamine mixture in ionic liquid

A novel task-specific ionic ligand with an imidazolium salt moiety was synthesized, and its catalytic ability and recyclability for asymmetric transfer hydrogenation of acetophenone derivatives with a formic acid-triethylamine azeotropic mixture in an ionic liquid [bmim][PF6] was examined.     

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.     

Iminophosphine-palladium(0) complexes as catalysts in the alkoxycarbonylation of terminal alkynes

In the presence of methanesulfonic acid, the palladium(0)-olefin complexes: [Pd(η²-ol)(P---N)] [ol=dimethyl fumarate or fumaronitrile, P---N=1-(Ph₂P)C₆H₄-2-CH=NR (R=CMe₃ or C₆H₄OMe-4)] catalyse the alkoxycarbonylation of terminal alkynes. Moderately good rates are obtained when the catalysts are promoted with two equivalents of the free P---N ligand and a large excess of acid at 120°C. The catalytic data suggest that derivatives of the type [Pd(alkyne)(P---N)_n] (n=2–3) are the active catalytic species.     

A copper- and solvent-free coupling of acid chlorides with terminal alkynes catalyzed by a polystyrene-supported palladium(0) complex under aerobic conditions

A polystyrene-supported palladium(0) complex [PS-dpp-Pd(0)] is an efficient catalyst for the copper- and solvent-free acylation of terminal alkynes with different acid chlorides in the presence of triethylamine as base, giving the corresponding ynones in good yields.