Ionic Liquid [bmim][BF4] as a Green Medium for Passerini Reaction

The Passerini reaction, a three-component condensation reaction of carboxylic acid, aldehyde and isocyanide constructing an α-acyloxycarboxamide in a single step, was first discovered by Passerini about 80 years ago1. Since then, this reaction has been w…     

Recycling Chiral Organocatalyst （4S）-Phenoxy-（S）-proline for Direct Asymmetric Aldol Reaction in Ionic Liquid （bmim）PF6

Room temperature ionic liquid (bmim)PF6 was evaluated for recycling an organocatalyst (4S)-phenoxy-(S)-proline for direct asymmetric aldol reactions. The desired aldol products were obtained with good yields up to 93.2% and enantioselectivities up to 88.5%, and isolation of the products by simple extraction allowed recycling the ionic liquid containing the immobilized catalyst in subsequent reactions without significant decrease of yields and enantioselectivities.     

Sequential Aldol/Michael Addition Reaction in Ionic Liquid Catalyzed by Morpholine: A Convenient Synthesis of 1,3,5‐Triaryl‐1,5‐pentanedione

A series of 1,3,5‐triaryl‐1,5‐pentanediones was obtained via a sequential aldol condensation and Michael addition reaction in ionic liquid catalyzed by morpholine, as a one‐pot reaction. The significance of our findings relates to reducing the use of organic solvents, potentially toxic and hazardous materials, as well as its simplicity, good yields, mild conditions, and lower costs.     

One-step Synthesis of Dipyrromethanes in the Presence of Ionic Liquid [Hmim]BF4

Dipyrromethanes were obtained in moderate yields by the condensation of ketone and pyrrole in the presence of ionic liquid [Hmim]BF4 without using any strong acid and other organic solvent.     

Heck Reaction of Iodoarenes with Methyl Acrylate Catalyzed by Cyciopalladated Complexes of Tertiary Arylamines Immobilized in Ionic Liquid[ Bmim ] ^＋ BF4^-

Heck reaction of iodoarenes with methyl acrylate, catalyzed by cyclolmlladated complexes of tertiary arylamines, was investi-gated in ionic liquid 1-butyl-3-metylimidazolium tetratluorobo-rate ([Bmim] BF4^- ). The products can be isolated convenient-ly from the ionic liquid-catalyst system. The catalysts could be reused for more than 10 times still with satisfactory catalytic ac-tivity.     

Synthesis of Aryl Allyl Ether in the Recyclable Ionic Liquid [bmim]PF_6

Ionic liquids, especially imidazonium salts, have recently gained recognition as possible environmentally benign alternative chemical process solvents. This is mainly due to their nonvolatile nature, insolubility in some solvents as well as their ability to dissolve a wide range of organic and inorganic materials, allowing the ionic liquids easy recovery and recycling. Examples of their application in organic reactions have been summarized in a number of recent review articles. 1 Aryl allyl et…     

Ionic liquid [bmim][BF4] acts as solvent and promoter for synthesis of halo-containing N-arylphthalimides

A new synthetic process of N-arylphthalimide and halo-containing N-arylphthalimides through the reaction between phthalic anhydride and aromatic amines bearing halo groups in[bmim][BF_4]was described,ionic liquid[bmim][BF_4]acted as the dual role of solvent and promoter.     

Direct Formation of 2,3,5‐Trichloropyridine and its Nucleophilic Displacement Reactions in Ionic Liquid

Abstract

Reaction of trichloroacetaldehyde and acrylonitrile in the presence of a catalytic amount of copper (I) chloride in ionic liquid afforded 2,3,5‐trichloropyridine, fluorination of which with KF and CsF in ionic liquid afforded 3,5‐dichloro‐2‐fluoropyridine and 5‐chloro‐2,3‐dichloropyridine. Reaction of 2,3,5‐trichloropyridine, 3,5‐dichloro‐2‐fluoropyridine, or 5‐chloro‐2,3‐dichloropyride with 2‐(4‐hydroxyphenoxy)propionates in ionic liquid afforded the corresponding 2‐aryloxylpropionates in good yields.     

Organic Reactions in Ionic Liquids: Ionic Liquid‐Accelerated One‐Pot Synthesis of 2‐Arylimidazo[1,2‐a]pyrimidines

Abstract

The room‐temperature ionic liquid n‐butylpyridinium tetrafluoroborate (BPyBF₄) is used as a recyclable alternative to classical molecular solvents in the one‐pot synthesis of 2‐arylimidazo[1,2‐a]pyrimidines by reaction with ketones, [hydroxy(tosyloxy)iodo]benzene, and 2‐aminopyrimidine. Significant rate enhancements and improved yields have been observed.     

Heck Reaction of Iodoarenes with Methyl Acrylate Catalyzed by Cyclopalladated Complexes of Tertiary Arylamines Immobilized in Ionic Liquid [Bmim]~+BF_4~-

IntroductionAsoneofthemostimportantC—Cformationreactionsandone stepmethodforthearylationofolefins ,Heckre actionhasattractedmuchinterest.1However ,thereactionusuallyneedsarelativelylargeamountofpalladiumcata lyst (>1mol%)forsatisfactoryconversions .Recently ,avarietyofpalladacyclesincorporatingcyclometallatedphos phine ,2 phosphite ,3 carbene ,4 imine5andoxime6havebeenreported .Theuseofcatalystswithnitrogen basedligandswasdemonstratedtopossessveryhighactivity .Wehavereportedthecyclopalladat…     

DFT Study on the Origin of the Enantioselectivity of （S）-4-Hydroxylproline-Catalyzed Direct Aldol Reaction between Acetone and 4-Nitrobenzaldehyde

DFT-B3LYP calculations were carried out to study the enantioselectivity of the （S）-4-hydroxylproline-catalyzed direct aldol reaction between acetone and 4-nitrobenzaldehyde. Four transition structures associated with the stereo-controlling step of the reaction have been determined. They are corresponding to the anti and syn arrangements of the methylene moiety related to the carboxylic acid group in enamine intermediate and the si and re attacks to the aldehyde carbonyl carbon. The effect of DMSO solvent on the stereo-controlling step was investigated with polarized continuum model （PCM）. The computed energies of the transition states reveal the moderate enantioselectivity of the reaction.     

Quantum-Chemical Investigation of the Mechanism of Transfer of Fluorine in the Reaction of F‐TEDA‐BF4 with Dimethylenebicyclo[3.3.1]nonane

The mechanism of the reaction of the N-fluoro reagent FTEDABF₄ with dimethylenebicyclo[3.3.1]nonane was investigated by the semiempirical PM3 SCF MO method using the Cramer–Truhlar SM5.42R solvation model. It was shown that the mechanism of addition of the fluorine corresponds to classical S _N 2 nucleophilic substitution involving single-electron transfer synchronous with the cleavage–formation of C—F and N—F bonds.     

Organic Reactions in Ionic Liquids: Ionic Liquid Promoted Knoevenagel Condensation of Aromatic Aldehydes with (2‐Thio)Barbituric Acid

Abstract

The Knoevenagel condensation of aromatic aldehydes with (2‐thio)barbituric acid proceeded efficiently in reusable ionic liquids, EAN, BmimBF₄, and BmimPF₆ at room temperature in the absence of any catalyst with high yields.     

D,L‐Proline‐Catalyzed One‐Pot Synthesis of Pyrans and Pyrano[2,3‐c]pyrazole Derivatives by a Grinding Method under Solvent‐Free Conditions

D,L‐Proline was found to efficiently catalyze the one‐pot condensation of aromatic aldehydes, malononitrile, and dimedone (1,3‐cyclohexanedione or 3‐methyl‐1‐phenyl‐2‐pyrazolin‐5‐one) 2‐Amino‐3‐cycano‐4‐aryl‐7,7‐dimethyl‐5,6,7,8‐tetrahydrobenzo[b]pyrans and 6‐amino‐5‐cyano‐4‐aryl‐1,4‐dihydropyrano[2,3‐c]pyrazoles were synthesized by a grinding method under solvent‐free conditions. The reaction proceeded cleanly at room temperature to afford the products in good yields.     

Mild and Convenient Synthesis of 1,2‐Dihydroquinolines from Anilines and Acetone Catalyzed by Ytterbium(III) Triflate in Ionic Liquids

A mild, convenient, and efficient process has been developed for the synthesis of 2,2,4‐trimethyl‐1,2‐dihydroquinolines by the reaction of anilines with acetone catalyzed by ytterbium(III) triflate [Yb(OTf)₃] in ionic liquids. The catalyst and ionic liquids can be easily recovered and reused, making this method friendly and environmentally acceptable.     

Design and Syntheses of Novel Calix[4]crown: Calix[4]‐Dixanthates‐Crowns

Abstract

A series of novel calix[4]‐dixanthates‐crowns were designed and synthesized by the “1 + 1 condensation” of reacting calix[4]‐1,3‐dixanthate salts derivative (4) with polyethylene glycol ditosylates in 40–60% yields. It was found that the new calixcrowns showed outstanding complexation abilities towards soft cations. Calix[4]‐dixanthate‐crown‐4 (5b) exhibited high complexation selectivity towards Ni²⁺.     

Efficient Synthesis of 3,5,6‐Trisubstituted‐1,2,4‐triazines in the Brønsted Acidic Ionic Liquid, 1‐n‐Butylimidazolium Tetrafluoroborate ([Hbim]BF4)

3,5,6‐Trisubstituted‐1,2,4‐triazines were synthesized in a one‐pot reaction with acid hydrazide, 1,2‐diketone, and ammonium acetate in the Brønsted acidic ionic liquid, 1‐n‐butyl imidazolium tetrafluoroborate ([Hbim]BF₄).     

Multicomponent Reaction in Ionic Liquid： A Novel and Green Synthesis of 1, 4-Dihydropyridine Derivatives

1, 4-Dihydropyridine (DHP) heterocyclic ring is a common feature of various bioactivecompounds such as vasodilator, bronchodilator and antiatherosclerotic, antitumor, andantidiabetic agents1. Due to their important pharmacological activities, many methods…     

Copper‐Catalyzed Coupling Reaction of 2‐Thioxo‐4‐quinazolinone and Thieno[3,2‐d]pyrimidin‐4‐one Methane Sulphonamide with Aryl Iodides: Preparation of Potential COX‐2 Selective Inhibitors

Thio‐aryl methane sulfonamide derivatives of 4‐quinazolinone and thieno[2,3‐d]pyrimidin‐4‐one were synthesized using powdery copper/copper(I) iodide as catalyst; their structural elucidation is also reported. These derivatives were planned as sulfur bioisosteres of selective COX‐2 inhibitor drugs.     

Reaction of Imidazo[1,2‐a]pyridines with Aliphatic Aldehydes: A Simple and Efficient Method for the Preparation of Novel C‐3 Vinylic Derivativesof Imidazo[1,2‐a]pyridines

A simple and efficient method for the preparation of novel C‐3 vinylic derivatives of imidazo[1,2‐a]pyridines has been developed by the reaction of imidazo [1,2‐a]pyridines with appropriate aliphatic aldehydes in acetic acid in a sealed tube.