Ionophilic phosphonium-appended carbopalladacycle catalyst for Suzuki–Miyaura and Heck cross-coupling catalysis

2010 ◽  
Vol 88 (1) ◽  
pp. 27-34 ◽  
Author(s):  
Jocelyn J. Tindale ◽  
Paul J. Ragogna
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Catalyst Activity ◽  
Reaction Medium ◽  
Cross Coupling ◽  
Metal Catalyst ◽  
Phosphonium Salts ◽  
Transition Metal Catalyst ◽  
Imidazolium Ionic Liquids ◽  
Liquid Reaction

An ionic liquid, covalently tethered to an efficient transition-metal catalyst in the presence of an ionic liquid reaction medium, can utilize ionophilic interactions to improve catalyst activity, recyclability, and product isolation while decreasing catalyst leaching. Given the greater stability of phosphonium salts in comparison to imidazolium ionic liquids under basic conditions, phosphonium-tagged oxime carbopalladacycle salts were prepared and employed in both Heck and Suzuki–Miyaura reactions. The desired product was obtained in good yields for up to four catalyst cycles in the case of the Suzuki–Miyaura reaction. While taking advantage of the non-volatile nature of ionic liquids, the product was isolated through simple sublimation from the reaction mixture, eliminating issues associated with catalyst leaching, and the remaining ionic liquid solvent–catalyst mixture was ready for further catalysis.

scholarly journals Palladium-catalyzed Sonogashira coupling reactions in γ-valerolactone-based ionic liquids

2019 ◽  
Vol 15 ◽  
pp. 2907-2913 ◽  
Author(s):  
László Orha ◽  
József M Tukacs ◽  
László Kollár ◽  
László T Mika
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Reaction Medium ◽  
Cross Coupling ◽  
Environmental Efficiency ◽  
Coupling Reactions ◽  
Sonogashira Coupling ◽  
Mild Conditions ◽  
Palladium Catalyzed ◽  
Alternative Reaction Medium

It was demonstrated that the γ-valerolactone-based ionic liquid, tetrabutylphosphonium 4-ethoxyvalerate as a partially bio-based solvent can be utilized as alternative reaction medium for copper- and auxiliary base-free Pd-catalyzed Sonogashira coupling reactions of aryl iodides and functionalized acetylenes under mild conditions. Twenty-two cross-coupling products were isolated with good to excellent yields (72–99%) and purity (>98%). These results represent an example which proves that biomass-derived safer solvents can be utilized efficiently in common, industrially important transformations exhibiting higher chemical and environmental efficiency.

Acceleration of Baylis-Hillman reaction using ionic liquid supported organocatalyst

2021 ◽  
Vol 08 ◽  
Author(s):  
Vivek Srivastava
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Reaction Rate ◽  
Reaction Medium ◽  
Catalyst Loading ◽  
Catalyst Recycling ◽  
Catalytic Systems ◽  
Heterogeneous Catalytic ◽  
Highly Active ◽  
Low Catalyst Loading

Background: Baylis-Hillman reaction suffers from the requirement of cheap starting materials, easy reaction protocol, possibility to create the chiral center in the reaction product has increased the synthetic efficacy of this reaction, and high catalyst loading, low reaction rate, and poor yield. Objective: The extensive use of various functional or non-functional ionic liquids (ILs) with organocatalyst increases the reaction rate of various organic transformations as a reaction medium and as a support to anchor the catalysts. Methods: In this manuscript, we have demonstrated the synthesis of quinuclidine-supported trimethylamine-based functionalized ionic liquid as a catalyst for the Baylis-Hillman reaction. Results: We obtained the Baylis-Hillman adducts in good, isolated yield, low catalyst loading, short reaction time, broad substrate scope, accessible product, and catalyst recycling. N-((E,3S,4R)-5-benzylidene-tetrahydro-4-hydroxy-6-oxo-2H-pyran-3-yl) palmitamide was also successfully synthesized using CATALYST-3 promoted Baylis-Hillman reaction. Conclusion: We successfully isolated the 25 types of Baylis-Hillman adducts using three different quinuclidine-supported ammonium-based ionic liquids such as Et3AmQ][BF4] (CATALYST-1), [Et3AmQ][PF6] (CATALYST-2), and [TMAAmEQ][NTf2](CATALYST-3) as new and efficient catalysts. Tedious and highly active N-((E,3S,4R)-5-benzylidene-tetrahydro-4-hydroxy-6-oxo-2H-pyran-3-yl) palmitamide derivative was also synthesized using CATALYST-3 followed by Baylis-Hillman reaction. Generally, all the responses demonstrated higher activity and yielded high competition with various previously reported homogenous and heterogeneous Catalytic systems. Easy catalyst and product recovery followed by six catalysts recycling were the added advantages of the prosed catalytic system.

scholarly journals The Influence of the Nature of Redox-Active Moieties on the Properties of Redox-Active Ionic Liquids and on Their Use as Electrolyte for Supercapacitors

Energies ◽  
2021 ◽  
Vol 14 (19) ◽  
pp. 6344
Author(s):  
Philipp S. Borchers ◽  
Patrick Gerlach ◽  
Yihan Liu ◽  
Martin D. Hager ◽  
Andrea Balducci ◽  
...  
Keyword(s):  
Phase Transition ◽  
Differential Scanning Calorimetry ◽  
Ionic Liquid ◽  
Ionic Liquids ◽  
Binary Mixtures ◽  
Thermal Characteristics ◽  
The Other ◽  
Scanning Calorimetry ◽  
Imidazolium Ionic Liquids ◽  
Redox Active

In this work, two new redox-active ionic liquids, one based on 2,2,6,6-tetramethylpiperidine-N-oxide and the other based on 4,4′-bipyridine, are synthesized and characterized. A ferrocene-based redox-active ionic liquid is used for referencing the results. All ionic liquids are formed via salt-metathesis from halogenate to bis(trifluoromethylsulfonyl)imide. Their fundamental thermal characteristics are assessed with differential scanning calorimetry. While the imidazolium ionic liquids show no melting point, the phase transition is well observable for the viologen-based ionic liquid. The properties of the neat redox-active ionic liquids and of binary mixtures containing these ionic liquids (0.1 m) and 1-butyl-1-methyl pyrrolidinium-bis(trifluoromethylsulfonyl)imide have been investigated. Finally, the use of these binary mixtures in combination with activated carbon-based electrodes has been considered in view of the use of these redox-active electrolytes in supercapacitors.

scholarly journals Zinc Acetate Immobilized on Mesoporous Materials by Acetate Ionic Liquids as Catalysts for Vinyl Acetate Synthesis

2015 ◽  
Vol 2015 ◽  
pp. 1-5 ◽  
Author(s):  
Hang Xu ◽  
Tianlong Yu ◽  
Mei Li
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Vinyl Acetate ◽  
Silica Gel ◽  
Catalyst Activity ◽  
Catalyst Layer ◽  
Space Velocity ◽  
Molar Ratio ◽  
Vinyl Acetate Monomer ◽  
Adsorption Desorption

Ionic liquid containing active ingredient Zn(CH3COO)2was loaded in mesoporous silica gel to form supported ionic liquids catalyst (SILC) which was used to synthesize vinyl acetate monomer (VAM). SILC was characterized by1HNMR, FT-IR, TGA, BET, and N2adsorption/desorption and the acetylene method was used to evaluate SILC catalytic activity and stability in fixed reactor. The result shows that 1-allyl-3-acetic ether imidazole acetate ionic liquid is successfully fixed within mesoporous channel of silica gel. The average thickness of ionic liquid catalyst layer is about 1.05 nm. When the catalytic temperature is 195°C, the acetic acid (HAc) conversion is 10.9% with 1.1 g vinyl acetate yield and 98% vinyl acetate (VAc) selectivity. The HAc conversion is increased by rise of catalytic temperature and molar ratio of C2H2 : HAc and decreased by mass space velocity (WHSV). The catalyst activity is not significantly reduced within 7 days and VAc selectivity has a slight decrease.

scholarly journals Ionic Liquid Catalyzed Per-O-Acetylation and Benzylidene Ring-Opening Reaction

Catalysts ◽  
2020 ◽  
Vol 10 (6) ◽  
pp. 642 ◽  
Author(s):  
Mayur Thul ◽  
Yao-Peng Wu ◽  
Yi-Jyun Lin ◽  
Shu-Lin Du ◽  
Hsin-Ru Wu ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Ring Opening ◽  
Room Temperature ◽  
Catalytic Amount ◽  
Atom Economy ◽  
Selective Catalyst ◽  
Imidazolium Ionic Liquids ◽  
Ring Opening Reaction ◽  
Brönsted Acid

Tunable aryl imidazolium ionic liquids acting as Brønsted acid ionic liquids were found to be efficient catalysts for per-O-acetylation and reductive ring opening of benzylidene acetals. This method requires a truly catalytic amount of the least expensive available ionic liquids that are water-stable and reusable and also stable at room temperature. The reactions were obtained in one hour with good to excellent yields. These reactions can form C−O and C−H bonds with a high atom economy. Furthermore, the ionic liquid is an anomeric selective catalyst in per-O-acetylation and reductive ring opening of benzylidene acetals of sugar moieties.

Distillable ionic liquids for a new multicomponent reaction

2007 ◽  
Vol 79 (11) ◽  
pp. 1869-1877 ◽  
Author(s):  
Anthony E. Rosamilia ◽  
Christopher R. Strauss ◽  
Janet L. Scott
Keyword(s):  
Carbon Dioxide ◽  
Ionic Liquid ◽  
Ionic Liquids ◽  
Multicomponent Reaction ◽  
Reaction Medium ◽  
Building Blocks ◽  
Substituted Anilines ◽  
Reaction Sequence ◽  
Unsaturated Ketones ◽  
Direct Preparation

Adducts of dimethylamine and carbon dioxide form a "distillable ionic liquid" (DIMCARB) that may used as both a reaction medium and catalyst in the direct, atom-economical synthesis of useful synthetic building blocks, such as mono-condensed α,β-unsaturated ketones. The utilization of such building blocks in the synthesis of two new classes of versatile macrocycles, by a sequence of condensation reactions (H2O by-product), is described. Investigation into the mechanism of action of DIMCARB catalysis and observation of an aniline impurity arising from a competing reaction sequence led to development of a new multicomponent reaction for the direct preparation of 2- or 4-substituted anilines. Some of the macrocycles and anilines are, respectively, supramolecular host compounds and ligands for the preparation of metal complexes.

scholarly journals 2D assemblies of ionic liquid crystals based on imidazolium moieties: formation of ion-conductive layers

2015 ◽  
Vol 39 (6) ◽  
pp. 4471-4477 ◽  
Author(s):  
Junji Sakuda ◽  
Masafumi Yoshio ◽  
Takahiro Ichikawa ◽  
Hiroyuki Ohno ◽  
Takashi Kato
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Liquid Crystals ◽  
Ionic Conductivity ◽  
Imidazolium Ionic Liquids ◽  
Ionic Liquid Crystals

Organization of imidazolium ionic liquids into 2D ion-conductive pathways enhances the ionic conductivity of the imidazolium-based ionic liquid crystals.

Plasmonic behavior of ionic liquid stabilized gold nanoparticles in molecular solvents

2017 ◽  
Vol 41 (21) ◽  
pp. 12989-12995 ◽  
Author(s):  
Sachin Thawarkar ◽  
Balu Thombare ◽  
Nageshwar D. Khupse
Keyword(s):  
Gold Nanoparticles ◽  
Ionic Liquid ◽  
Ionic Liquids ◽  
Surface Plasmon Resonance ◽  
Dielectric Properties ◽  
Surface Plasmon ◽  
Plasmon Resonance ◽  
Facile Synthesis ◽  
Imidazolium Ionic Liquids ◽  
Molecular Solvents

In this paper, we have demonstrated the facile synthesis of stable gold nanoparticles (AuNPs) using imidazolium ionic liquids (ImILs) as a stabilizer as well as a surfactant and their surface plasmon resonance (SPR) in different molecular solvents with varying dielectric properties.

A Phosphine-mediated Synthesis of 2,3,4,5-tetra-substituted Nhydroxypyrroles from α-oximino Ketones and Dialkyl Acetylenedicarboxylates Under Ionic Liquid Green-media

2018 ◽  
Vol 21 (1) ◽  
pp. 14-18
Author(s):  
Ashraf S. Shahvelayati ◽  
Maryam Ghazvini ◽  
Khadijeh Yadollahzadeh ◽  
Akram S. Delbari
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Organic Solvents ◽  
Condensation Reaction ◽  
Reaction Medium ◽  
Sustainable Chemistry ◽  
Polyfunctional Compounds ◽  
High Yields ◽  
Work Up ◽  
Reaction Media

Background: The development of multicomponent reactions (MCRs) in the presence of task-specific ionic liquids (ILs), used not only as environmentally benign reaction media, but also as catalysts, is a new approach that meet with the requirements of sustainable chemistry. In recent years, the use of ionic liquids as a green media for organic synthesis has become a chief study area. This is due to their unique properties such as non-volatility, non-flammability, chemical and thermal stability, immiscibility with both organic compounds and water and recyclability. Ionic liquids are used as environmentally friendly solvents instead of hazardous organic solvents. Objective: We report the condensation reaction between α-oximinoketone and dialkyl acetylene dicarboxylate in the presence of triphenylphosphine to afford substituted pyrroles under ionic liquid conditions in good yields. Result: Densely functionalized pyrroles was easily prepared from reaction of α-oximinoketones, dialkyl acetylene dicarboxylate in the presence of triphenylphosphine in a quantitative yield under ionic liquid conditions at room temperature. Conclusion: In conclusion, ionic liquids are indicated as a useful and novel reaction medium for the selective synthesis of functionalized pyrroles. This reaction medium can replace the use of hazardous organic solvents. Easy work-up, synthesis of polyfunctional compounds, decreased reaction time, having easily available-recyclable ionic liquids, and good to high yields are advantages of present method.

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