Synthesis of (−)‐3‐Carene‐2,5‐dione via Allylic Oxidation of (+)‐3‐Carene

Activated carbon‐supported CuCl₂ (CuCl₂/AC) is a heterogeneous catalyst for the liquid‐phase selective allylic oxidation of (+)‐3‐carene with tert‐butyl hydroperoxide (TBHP) and O₂ to produce (?)‐3‐carene‐2,5‐dione. The possible reaction mechanism and the effects of different factors on the allylic oxidation were investigated. The optimal conditions are as follows: reaction temperature, 45 °C; molar ratio of CuCl₂ to (+)‐3‐carene, 1%; volume ratio of (+)‐3‐carene to TBHP, 1:3; and reaction time, 12 h. Under the optimal conditions, the conversion of (+)‐3‐carene reached 100%, whereas the selectivity for (?)‐3‐carene‐2,5‐dione reached 78%. The CuCl₂/AC catalyst was characterized via X‐ray diffraction, and the chemical structure of the target compound was identified via infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, mass spectrometry, and optical analysis.     

Copper‐Polymer Nanocomposite Catalyst for Synthesis of 1,4‐Diphenylbutadiyne‐1,3

A new catalyst for cross‐coupling synthesis of 1,4‐diphenylbutadiyne‐1,3 was prepared by thermolysis of copper(II) poly‐5‐vinyltetrazolate. It presents heterogeneous catalyst, in which copper nanoparticles are supported on polymeric matrix surface. The catalyst is recovered, recycled, and shows high catalytic activity in cross‐coupling synthesis of 1,4‐diphenylbutadiyne‐1,3. The reaction proceeds in aerobic conditions at room temperature in the presence of pyridine.     

Polymerization of conjugated 5‐[(5‐ethynyl‐1‐naphthyl)ethynyl]‐N,N‐dimethylnaphthalen‐1‐amine with rhodium and palladium complexes

The monomer 5‐[(5‐ethynyl‐1‐naphthyl)ethynyl]‐N,N‐dimethylnaphthalen‐1‐amine was satisfactory obtained through the heterocoupling reaction of 5‐ethynyl‐N,N‐dimethylnaphthalen‐1‐amine and 4‐(5‐iodo‐1‐naphthyl)‐2‐methyl‐3‐butyn‐2‐ol catalyzed by a palladium–copper system, followed by acetone elimination. Poly{5‐[(5‐ethynyl‐1‐naphthyl)ethynyl]‐N,N‐dimethylnaphthalen‐1‐amine} was obtained through the reaction of the acetylene monomer with homogeneous rhodium and palladium catalyst complexes. The structure of the polymers always showed a trans–cisoidal chain configuration on the basis of IR and NMR spectra. Moreover, only for the rhodium catalyst complex in methanol was a dimeric product isolated in a very low yield, having a conjugated terminal ene–yne structure, which permitted the consideration of a metallated chain‐transfer intermediate in the polymer propagation. The mass determination of the polymers, by osmometry and gel permeation chromatography techniques, showed low average molecular weights. The kinetics of the catalyzed polymerization were analyzed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2038–2047, 2007     

Synthesis of 4‐((2‐hydroxynaphthalen‐1‐yl)(aryl)methyl)‐5‐methyl‐2‐phenyl‐1H‐pyrazol‐3(2H)‐ones using nano‐Zn‐[2‐boromophenyl‐salicylaldimine‐methylpyranopyrazole]Cl2 nanoparticles

Nano‐Zn‐[2‐boromophenyl‐salicylaldimine‐methylpyranopyrazole]Cl₂ (nano‐[Zn‐2BSMP]Cl₂) as a nanoparticle Schiff base complex and a catalyst was introduced for the solvent‐free synthesis of 4‐((2‐hydroxynaphthalen‐1‐yl)(aryl)methyl)‐5‐methyl‐2‐phenyl‐1H‐pyrazol‐3(2H)‐ones by the multicomponent condensation reaction of various aromatic aldehydes, β‐naphthol, ethyl acetoacetate, and phenyl hydrazine at room temperature.     

Efficient One‐pot Synthesis of Alkyl 3‐(alkyl)‐4‐methyl‐2‐thioxo‐2,3‐dihydrothiazole‐5‐carboxylates in a Multi Component Reaction

A simple and efficient one‐pot synthesis of alkyl 2‐(alkyl)‐4‐methyl‐2‐thioxo‐2,3‐dihydrothiazole‐5‐carboxylates from the reaction of primary alkylamines and carbon disulfide in the presence of 2‐chloro‐1,3‐dicarbonyl compounds is described. This new protocol has several advantages such as lack of necessity of the catalyst, good yields, mild conditions and short times for reaction.     

Transition‐metal‐catalyzed reactions of 5‐methylene‐2‐oxazolidinone and 5‐methylene‐1,3‐thiazolidine‐2‐thione with isocyanates

5‐Methylene‐2‐oxazolidinone (1) and 5‐methylene‐1,3‐thiazolidine‐2‐thione (4) react with various isocyanates to give the corresponding urethanes 3 and 5 in high yields in the presence of palladium(0) or palladium(II) catalyst under mild reaction conditions. A mechanism is proposed. Copyright © 2003 John Wiley & Sons, Ltd.     

Efficient Synthesis of Oxazolidin‐2‐one via (Chitosan‐Schiff Base)cobalt(II)‐Catalyzed Oxidative Carbonylation of 2‐Aminoalkan‐1‐ols

The (chitosan‐Schiff base)cobalt(II) complex was found to be an efficient catalyst for the oxidative carbonylation (CO/O₂) of 2‐aminoalkan‐1‐ols 1 to give oxazolidin‐2‐ones 2 , in the presence of NaI. The effects of promoters, temperature, solvents, and other reaction conditions were investigated in this study.     

Isocyanide‐Based Three‐Component Synthesis of Highly Substituted 1,6‐Dihydro‐6,6‐dimethylpyrazine‐2,3‐dicarbonitrile, 3,4‐Dihydrobenzo[g]quinoxalin‐2‐amine,and 3,4‐Dihydro‐3,3‐dimethyl‐quinoxalin‐2‐amine Derivatives

A novel and efficient isocyanide‐based multicomponent reaction between alkyl or aryl isocyanides 1 , 2,3‐diaminomaleonitrile ( 2 ), naphthalene‐2,3‐diamines ( 6 ) or benzene‐1,2‐diamine ( 9 ), and 3‐oxopentanedioic acid ( 3 ) or Meldrum's acid ( 4 ) or ketones 7 was developed for the ecologic synthesis, at room temperature under mild conditions, of 1,6‐dihydropyrazine‐2,3‐dicarbonitriles 5a – 5f in H₂O without using any catalyst, and of 3,4‐dihydrobenzo[g]quinoxalin‐2‐amine and 3,4‐dihydro‐3,3‐dimethyl‐quinoxalin‐2‐amine derivatives 8a – 8g and 10a – 10e , respectively, in the presence of a catalytic amount of p‐toluenesulfonic acid (TsOH) in EtOH, in good to excellent yields (Scheme 1).     

Solvent‐free Synthesis of 1,8‐Dioxo‐octahydroxanthenes and Tetra‐hydrobenzo[a]xanthene‐11‐ones over Poly(N,N′‐dibromo‐N‐ethylnaphtyl‐2,7‐sulfonamide)

In this work, poly(N,N ′‐dibromo‐N ‐ethylnaphtyl‐2,7‐sulfonamide) (PDNES ) as a highly efficient catalyst was applied for the synthesis of 1,8‐dioxo‐octahydroxanthenes and tetra‐hydrobenzo[a]xanthene‐11‐ones under neutral and solvent‐free conditions.     

Unexpected Spiroproducts from the Reaction of N‐Benzoylglycine with Ortho‐Formylbenzoic Acids −3,5′‐Dioxo‐2′‐Phenyl‐1,3‐Dihydrospiro[Indene‐2,4′‐[1,3]Oxazol]‐1‐yl Acetates: Establishments of Their Structure

This paper describes a method of preparation of new 3,5′‐dioxo‐2′‐phenyl‐1,3‐dihydrospiro[indene‐2,4′‐[1,3]oxazol]‐1‐yl acetate and its 5‐chloro‐ and bromoderivatives as products of interaction of N‐benzoylglycine (hippuric acid) with corresponding ortho‐formylbenzoic acids. The reaction carried out in acetic anhydride media in the presence of piperidine as catalyst. The novel spirocompounds were purified by column chromatography from multicomponent reaction mixtures. The composition of the spiro‐products was confirmed by C, H, N element analysis. The structure was established by IR, MS, ¹H‐ and ¹³C‐NMR analysis including COSY ¹H‐¹³C experiments.     

Trans‐3,5‐dihydroperoxy‐3,5‐dimethyl‐1,2‐dioxalane/HBr System as New,Effective, Mild and Non‐toxic Reagent for Synthesis of 2‐Aryl‐1H‐benzothiazoles and 2‐Aryl‐1‐arylmethyl‐1H‐benzimidazoles

Ttrans‐3,5‐dihydroperoxy‐3,5‐dimethyl‐1,2‐dioxalane has been used as new, effective, solid, inexpensive and nontoxic oxidant for in situ generation of Br⁺ from HBr. This system has been applied as catalyst for synthesis of 2‐aryl‐1H‐benzothiazoles and 2‐aryl‐1‐arylmethyl‐1H‐benzimidazoles at room temperature in excellent yields and high purity.     

Ultrasound‐Promoted Catalyst‐Free Synthesis of 2,2′‐(1,4‐Phenylene)bis[1‐acetyl‐1,2‐dihydro‐4H‐3,1‐benzoxazin‐4‐one] Derivatives

A convenient approach to 2,2′‐(1,4‐phenylene)bis[1‐acetyl‐1,2‐dihydro‐4H‐3,1‐benzoxazin‐4‐one] derivatives 4 was explored employing the one‐pot condensation of anthranilic acids (=2‐aminobenzoic acids) 1 with terephthalaldehyde (=benzene‐1,4‐dicarboxaldehyde; 2 ) under ultrasound‐irradiation conditions (Scheme 1). The reactions proceeded smoothly in the presence of excess Ac₂O in the absence of any other catalyst and solvent to afford the respective products in high yields.     

Ferrocene‐tagged ionic liquid stabilized on silica‐coated magnetic nanoparticles: Efficient catalyst for the synthesis of 2‐amino‐3‐cyano‐4H‐pyran derivatives under solvent‐free conditions

An advanced novel magnetic ionic liquid based on imidazolium tagged with ferrocene, a supported ionic liquid, is introduced as a recyclable heterogeneous catalyst. Catalytic activity of the novel nanocatalyst was investigated in one‐pot three‐component reactions of various aldehydes, malononitrile and 2‐naphthol for the facile synthesis of 2‐amino‐3‐cyano‐4H‐pyran derivatives under solvent‐free conditions without additional co‐catalyst or additive in air. For this purpose, we firstly synthesized and investigated 1‐(4‐ferrocenylbutyl)‐3‐methylimidazolium acetate, [FcBuMeIm][OAc], as a novel basic ferrocene‐tagged ionic liquid. This ferrocene‐tagged ionic liquid was then linked to silica‐coated nano‐Fe₃O₄ to afford a novel heterogeneous magnetic nanocatalyst, namely [Fe₃O₄@SiO₂@Im‐Fc][OAc]. The synthesized novel catalyst was characterized using ¹H NMR, ¹³C NMR, Fourier transform infrared and energy‐dispersive X‐ray spectroscopies, X‐ray diffraction, and transmission and field emission scanning electron microscopies. Combination of some unique characteristics of ferrocene and the supported ionic liquid developed the catalytic activity in a simple, efficient, green and eco‐friendly protocol. The catalyst could be reused several times without loss of activity.     

Melamine Trisulfunic Acid: An Efficient and Recyclable Solid Acid Catalyst for the Synthesis of 4,4′‐(Arylmethylene)‐bis‐(1H‐pyrazol‐5‐ols)

Melamine trisulfunic acid is employed as a recyclable catalyst for the condensation reaction of aromatic aldehydes with 3‐methyl‐l‐phenyl‐2‐pyrazolin‐5‐one. This condensation reaction was performed in ethanol under refluxing conditions giving 4,4′‐(arylmethylene)‐bis‐(3‐methyl‐1‐phenyl‐1H‐pyrazol‐5‐ols) in 80‐96% yields.     

Eco‐friendly synthesis of 3,4‐dihydroquinoxalin‐2‐amine,diazepine‐tetrazole and benzodiazepine‐2‐carboxamide derivatives with the aid of MCM‐48/H5PW10V2O40

A heterogeneous material composed of MCM‐48/H₅PW₁₀V₂O₄₀ was produced and used as an efficient, eco‐friendly and highly recyclable catalyst for the one‐pot and multicomponent synthesis of 3,4‐dihydroquinoxalin‐2‐amine, diazepine‐tetrazole and benzodiazepine‐2‐carboxamide derivatives in aqueous media and at room temperature with high yields in short reaction times (40–60 min). The recoverable catalyst was easily recycled at least five times without any loss of catalytic activity. The structures of obtained products were confirmed using ¹H NMR and ¹³C NMR spectra.     

Highly efficient Pd‐PEPPSI‐IPr catalyst for N‐(4‐pyridazinyl)‐bridged bicyclic sulfonamides via Suzuki–Miyaura coupling reaction

A protocol for the Suzuki–Miyaura coupling of novel 2‐(6‐chloropyridazin‐3‐yl)‐5‐(aryl/heteroarylsulfonyl)‐2,5‐diazabicyclo[2.2.1]heptanes and heteroarylboronic acids to afford variety of coupled products was realized. Pd‐PEPPSI‐IPr catalyst was found to be a powerful and reusable catalyst under relatively mild reaction conditions.     

Copper nanoparticles supported on 2‐methoxy‐1‐phenylethanone‐functionalized MCM‐41: An efficient and recyclable catalyst for one‐pot three‐component C–S coupling reaction of aryl halides with benzyl bromide and thiourea

An environmentally friendly copper‐based catalyst supported on 2‐methoxy‐1‐phenylethanone‐functionalized MCM‐41 was prepared and characterized by Fourier transform‐infrared, transmission electron microscopy, field emission‐scanning electron microscopy, X‐ray diffraction and inductively coupled plasma techniques. The catalyst was applied for the one‐pot three‐component C–S coupling reactions of aryl halides with benzyl bromide and thiourea under aerobic conditions to afford the corresponding coupled products in good yields in water. The catalyst could be recovered and recycled five times. These results prove 2‐methoxy‐1‐phenylethanone‐functionalized MCM‐41 supported Cu (II) complex was not leached during the reaction. Also it shows the correct heterogeneous nature of the catalyst.     

Novel nano molten salt tetra‐2,3‐pyridiniumporphyrazinato‐oxo‐vanadium tricyanomethanide as a vanadium surface‐free phthalocyanine catalyst: Application to Strecker synthesis of α‐aminonitrile derivatives

Efficient and recyclable novel nano tetra‐2,3‐pyridiniumporphyrazinato‐oxo‐vanadium tricyanomethanide, {[VO(TPPA)][C(CN)₃]₄}, as a vanadium surface‐free phthalocyanine‐based molten salt catalyst was successfully designed, produced and used for the Strecker synthesis of α‐aminonitrile derivatives through a one‐pot three‐component reaction between aromatic aldehydes, trimethylsilyl cyanide and aniline derivatives under neat conditions at 50 °C. This catalyst was well characterized using Fourier transform infrared, UV–visible, X‐ray photoelectron and energy‐dispersive X‐ray spectroscopies, X‐ray diffraction, scanning and high‐resolution transmission electron microscopies, inductively coupled plasma mass spectrometry and thermogravimetric analysis. The catalyst can be simply recovered and reused several times without significant loss of catalytic activity.     

One‐Pot Synthesis of 4‐(2,3‐Dihydro‐2‐hydroxy‐1,3‐dioxo‐1H‐inden‐2‐yl)‐Substituted 1‐Aryl‐1H‐pyrazole‐3‐carboxylates via a Tandem Three‐Component Reaction

The hitherto unreported, highly functionalized 1H‐pyrazole‐3‐carboxylates 3 have been synthesized in good yields via a one‐pot three‐component domino reaction of phenylhydrazines, dialkyl acetylenedicarboxylates, and ninhydrin under mild conditions for the first time. No co‐catalyst or activator is required for this multicomponent reaction, and the reaction is, from an experimental point of view, simple to perform (Scheme 1). The structures of compounds 3 were corroborated spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS) and by elemental analyses. A plausible mechanism for this type of cyclization/addition reaction is proposed (Scheme 2).     

Mizoroki–Heck and Suzuki–Miyaura reactions mediated by poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)‐stabilized magnetically separable palladium catalyst

The purpose of this work was to synthesize and characterize a new magnetic polymer nanosphere‐supported palladium(II) acetate catalyst for reactions requiring harsh conditions. In this regard, an air‐stable, moisture‐stable and highly efficient heterogenized palladium was synthesized by the coordination of palladium(II) acetate with poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)‐grafted modified magnetic nanoparticles with a core–shell structure. The structure of the newly developed catalyst was characterized using various techniques. The catalytic activity of the resultant nano‐organometallic catalyst was evaluated in Mizoroki–Heck and Suzuki–Miyaura reactions to afford the corresponding coupling products in good to excellent yields. High selectivity as well as outstanding turnover number (14 143, 4900) and turnover frequency (28 296, 7424) values were recorded for the catalyst in Suzuki–Miyaura and Mizoroki–Heck reactions, respectively. Magnetic separation and recycling of the catalyst for at least six runs became possible without any significant loss of efficiency or any detectable palladium leaching.