Efficient regio- and stereo-selective cleavage of aziridines and epoxides using an ionic liquid as reagent and reaction medium

2007 ◽  
Vol 85 (5) ◽  
pp. 366-371 ◽  
Author(s):  
Brindaban C Ranu ◽  
Laksmikanta Adak ◽  
Subhash Banerjee
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Organic Solvent ◽  
Reaction Medium ◽  
Synthetic Route ◽  
High Yields

Ionic liquids, containing a variety of functionalities such as halo, azido, and thiocyano, efficiently cleave aziridines and epoxides to the corresponding products in high yields. The cleavages are regio- and stereo-selective. The reactions are complete in 1 h at 60 °C and do not require any other catalyst or organic solvent. Thus, a convenient synthetic route to 1,2-haloamines, 1,2-azidoamines, 1,2-thiocyanoamines, 1,2-azidoalcohols, and 1,2-thiocyanoalcohols is developed.Key words: aziridine, epoxide, ionic liquid, cleavage, regioselectivity, stereoselectivity

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.

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.

Ionic liquid promoted and mediated green preparation of arylbispyranylmethane and pyran derivatives and their hybrid with a pyrimidine nucleoside

2009 ◽  
Vol 2009 (8) ◽  
pp. 473-477 ◽  
Author(s):  
Xinying Zhang ◽  
Yingying Qu ◽  
Xuesen Fan ◽  
Xia Wang ◽  
Jianji Wang
Keyword(s):  
Ionic Liquid ◽  
High Efficiency ◽  
Reaction Medium ◽  
Environmentally Benign ◽  
Pyrimidine Nucleoside ◽  
Reaction Conditions ◽  
Operation Process ◽  
Antiviral Activities ◽  
Benign Nature ◽  
High Yields

The utilisation of an ionic liquid-[bmim][BF4] as both reaction medium and promoter for the reaction between aldehyde and 4-hydroxy-6-methylpyran-2-one is described. Without any added catalyst, this reaction was realised efficiently to give arylbispyranylmethane derivatives in high yields. Alternatively, when this reaction was carried out in the presence of acetic anhydride, fused pyran derivatives were obtained. These two novel procedures have advantages such as an environmentally benign nature, high efficiency, simple operation process and mild reaction conditions. As an application, these procedures were used in the preparation of novel 5-substituted pyrimidine nucleoside derivatives with potential antiviral activities.

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.

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.

One Pot Three Component Synthesis of 9-arylpolyhydroacridine Derivatives in an Ionic Liquid Medium

2005 ◽  
Vol 2005 (9) ◽  
pp. 600-602 ◽  
Author(s):  
Yu-Ling Li ◽  
Mei-Mei Zhang ◽  
Xiang-Shan Wang ◽  
Da-Qing Shi ◽  
Shu-Jiang Tu ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Ammonium Acetate ◽  
Aromatic Aldehydes ◽  
Environmentally Benign ◽  
Reaction Conditions ◽  
One Pot ◽  
High Yields ◽  
Work Up ◽  
Ionic Liquid Medium

In this paper the preparation of 3,3,6,6-tetramethyl-9-aryl-1,2,3,4,5,6,7,8,9,10- decahydroacridin-1,8-dione derivatives from aromatic aldehydes, 5,5-dimethyl-1,3- cyclohexanedione and ammonium acetate in ionic liquids [bmim+][BF4-] is described. This new method has the advantages of easier work-up, milder reaction conditions, high yields and an environmentally benign procedure compared with other methods.

Synthesis of 3-O-Caffeoyl-Quinide Catalyzed by p-Toluenesulfonic Acid

2014 ◽  
Vol 1033-1034 ◽  
pp. 39-42
Author(s):  
Jun Wang ◽  
Sha Sha Wang ◽  
Xiang Yang Wu
Keyword(s):  
Ionic Liquid ◽  
Organic Solvent ◽  
Intermediate Product ◽  
Reaction Medium ◽  
Purification Method ◽  
Nmr Spectrum ◽  
H Nmr ◽  
Caffeoylquinic Acid ◽  
Toluenesulfonic Acid

3-O-caffeoyl-quinide, a dehydration compound of 3-O-caffeoylquinic acid, was obtained usingp-toluenesulfonic acid as a catalyst via esterification in traditional organic solvent and transesterification in ionic liquid, respectively. The quinide, identified by1H-NMR spectrum, was prepared as an intermediate product for the synthesis of 3-O-caffeoyl-quinide, and the products was identified by LC-MS. Results indicated that the developed purification method of quinide was much simple than before with a higher yield, and [Bmim][Tf2N] was selected as the suitable reaction medium.

scholarly journals Grubbs–Hoveyda type catalysts bearing a dicationic N-heterocyclic carbene for biphasic olefin metathesis reactions in ionic liquids

2015 ◽  
Vol 11 ◽  
pp. 1632-1638 ◽  
Author(s):  
Maximilian Koy ◽  
Hagen J Altmann ◽  
Benjamin Autenrieth ◽  
Wolfgang Frey ◽  
Michael R Buchmeiser
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Organic Solvent ◽  
Single Crystal ◽  
Ring Opening ◽  
The Novel ◽  
Metathesis Polymerization ◽  
X Ray ◽  
Metathesis Catalyst ◽  
Nonpolar Organic

The novel dicationic metathesis catalyst [(RuCl2(H2ITapMe2)(=CH–2-(2-PrO)-C6H4))2+ (OTf−)2] (Ru-2, H2ITapMe2 = 1,3-bis(2’,6’-dimethyl-4’-trimethylammoniumphenyl)-4,5-dihydroimidazol-2-ylidene, OTf− = CF3SO3 −) based on a dicationic N-heterocyclic carbene (NHC) ligand was prepared. The reactivity was tested in ring opening metathesis polymerization (ROMP) under biphasic conditions using a nonpolar organic solvent (toluene) and the ionic liquid (IL) 1-butyl-2,3-dimethylimidazolium tetrafluoroborate [BDMIM+][BF4 −]. The structure of Ru-2 was confirmed by single crystal X-ray analysis.

scholarly journals Metal-Catalyzed Degradation of Cellulose in Ionic Liquid Media

Inorganics ◽  
2018 ◽  
Vol 6 (3) ◽  
pp. 78 ◽  
Author(s):  
Tiina Aid ◽  
Mihkel Koel ◽  
Margus Lopp ◽  
Merike Vaher
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Molybdenum Oxide ◽  
Cellulose Degradation ◽  
Biomass Conversion ◽  
Reaction Medium ◽  
Good Activity ◽  
Industrial Chemicals ◽  
Liquid Media ◽  
Metal Catalyzed

Biomass conversion to 5-hydroxymethylfurfural (HMF) has been widely investigated as a sustainable alternative to petroleum-based feedstock, since it can be efficiently converted to fuel, plastic, polyester, and other industrial chemicals. In this report, the degradation of commercial cellulose, the isomerization of glucose to fructose, and the conversion of glucose to HMF in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl]) using metal catalysts (CrCl3, ZnCl2, MgCl2) as well as tungsten and molybdenum oxide-based polyoxometalates (POM) were investigated. Tungsten and molybdenum oxide-based POMs in ionic liquids (IL) were able to degrade cellulose to majority glucose and epimerize glucose to mannose (in the case of the molybdenum oxide-based POM). A certain amount of glucose was also converted to HMF. The tungsten oxide-based POM in IL showed good activity for cellulose degradation but the overall products yield remained 28.6% lower than those obtained using CrCl3 as a catalyst. Lowering the cellulose loading did not significantly influence the results and the addition of water to the reaction medium decreased the product yields remarkably.

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.

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