A sequential synthesis of substituted furans from aryl alkynes and ketones involving a cerium(IV) ammonium nitrate (CAN)-mediated oxidative cyclization

A convenient, two-step synthesis of substituted furans from readily available aryl alkynes and ketones is reported. The furan-forming oxidative cyclization is mediated by the combination of cerium(IV) ammonium nitrate and potassium bromide and can be carried out in an open flask.     

Cerium(IV)ammonium nitrate(CAN)initiated O-alkylation of oximes with N-vinyl lactams

O-Alkylation of oximes with N-vinylpyrrolidin-2-one or iV-methyl-N-vinylacetamide was efficiently initiated by a catalytic amount of cerium(IV)ammonium nitrate(CAN), giving the corresponding oxime ether derivatives in good yield.     

Cerium(IV) ammonium nitrate: Reagent for the versatile oxidative functionalization of styrenes using N-hydroxyphthalimide

Cerium(IV) ammonium nitrate was found to be a versatile reagent for the oxidative functionalization of styrenes using N-hydroxyphthalimide and iodine affording three different types of products with oxyphthalimide, nitrate and iodide groups. It was shown that reaction of styrenes with N-hydroxyphthalimide and cerium(IV) ammonium nitrate can be selectively directed to oxynitro-oxyphthalimides and dioxyphthalimides depending on the reaction conditions, in particular a solvent. Reaction of styrenes with iodine under the action of N-hydroxyphthalimide and cerium(IV) ammonium nitrate leads to the formation of iodo-oxyphthalimides.     

Nitrophenol Derivatives Oxidized by Cerium(IV) Ammonium Nitrate (CAN) and Their Cytotoxicity

Oxidation of a series of phenols with cerium(IV) ammonium nitrate (CAN) in acetonitrile under mild conditions yields the mixture of corresponding nitrophenols. In the cases of methylphenols and hydroxy ‐carboxylic acids, the steric effect may reduce the nitration reaction. Compounds 3a and 4b showed selective activities to Hep 3B and Hep G2 cancer cell lines, respectively. Compound 2c showed selective activities to Hep G2 and MDA‐MB‐231 cancer cell lines. Furthermore, compound 10b showed selective activities to Hep G2, Hep 3B, MCF‐7 and MDA‐MB‐231 cancer cell lines.     

Synthesis and antitumor activity of 6- and 2- （ 1-acyl sulfanylalkyl）-5,8-dimethoxy- 1,4-naphthoquinones

Sixteen novel 6- and 2-（1-acylsulfanylalkyl）-5,8-dimethoxy-l,4-naphthoquinones were designed and synthesized. Their cytotoxicities were evaluated in vitro against BEL-7402, HT-29 and SPC-Al cell lines. The pharmacological results showed that most of the prepared compounds displayed the excellent selectivity for HT-29 cell line. Compound lab exhibited the most potent antitumor activity among the tested compounds.     

Regioselective radical addition of 3-oxopropanenitriles with terminal dienes promoted by cerium(IV) ammonium nitrate and manganese(III) acetate

Radical addition of 3-oxopropanenitriles to 1,3-butadiene derivatives promoted by (NH₄)₂Ce(NO₂)₆ and Mn(OAc)₃ afforded 5-ethenyl-4,5-dihydrofuran-3-carbonitriles in low to good yields. These dihydrofurans were characterised by IR, ¹H-NMR, ¹³C-NMR and HRMS spectra. All radical additions performed via CAN and Mn(OAc)₃ were occurred on the terminal double bond on dienes. A mechanism for the formation of the dihydrofurans was proposed.     

Cerium(IV) ammonium nitrate catalyzed synthesis of α-dehydro-β-amino esters

α-Dehydro-β-amino esters have been synthesized regioselectively from acetates of Baylis-Hillman adducts with amines in the presence of a catalytic amount of ceric ammonium nitrate (CAN) in good yield. The regioselectivity does not differ with respect to the polarity of the solvent.     

Esterification‐nitration of Ortho‐hydroxyphenyl Carboxylic Acids and Benzoic Acids with Cerium(IV) Ammonium Nitrate (CAN)

A convenient and useful esterification was realized, and this reaction proceeded without a dehydrating reagent or water removal equipment. A series of ortho‐hydroxyphenyl carboxylic acids and benzoic acids were transformed to their corresponding methyl esters under CAN/CH₃OH reaction conditions. Whereas in an aprotic solvent, acetonitrile, sp³‐C tethered ortho‐hydroxyphenyl carboxylic acids undergo simultaneous o,p‐dinitration and intramolecular esterification reactions in good yields. Also, 2‐((1 E)‐2‐nitrovinyl)‐4‐nitro‐phenol ( 3e ) showed selective cytotoxicities toward MCF‐7, HEP G2, and HEP 3B cell lines with IC₅₀ values of 23.50, 7.33, and 7.59 ug/mL, respectively.     

Facile synthesis of 1,2,3-tricarbonyls from 1,3-dicarbonyls mediated by cerium(IV) ammonium nitrate

A mild and efficient protocol for the synthesis of vicinal tricarbonyl compounds from β-dicarbonyls in a single step using cerium(IV) ammonium nitrate as a catalytic oxidant is described. Ease of execution, wide substrate scope and the suitability for the synthesis of commercially important compounds like ninhydrin, alloxan and oxoline make this reaction particularly noteworthy.     

Ceric (IV) ammonium nitrate (CAN) mediated synthesis of pyrrole-2,3,4,5-tetracarboxylates by reaction of dimethyl acetylenedicarboxylate with an amine

A simple one-step method for efficient synthesis of pyrrole-2,3,4,5-tetracarboxylates by reaction of dimethyl acetylenedicarboxylate with an amine using ceric (IV) ammonium nitrate as one electron oxidant is described.     

Electron transfer reactions of 1-phenyl-4-vinylpyrazole mediated by cerium(IV) ammonium nitrate

Summary The title compound is converted into the cyclic ethers5 and the alcohol6 upon treatment with ceric ammonium nitrate in acetone. Using methanol as a solvent the dimethoxy derivative9 and the nitrate ester10 are formed. No cross cycloaddition is observed in the presence of olefins such as ethyl vinyl ether,DMAD, or indene; however, with cyclopentadiene as co-reagent a mixture of the exo-endo Diels-Alder adducts14 involving the vinylic system of 1 as 2 component is obtained. The results are rationalized through the interrnediacy of the radical cation1 ^·+, generated by single electron transfer (SET) from the neutral precursor1 to Ce(IV).

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Elektrontransfer-Reaktionen von 1-Phenyl-4-vinylpyrazol mittels Cer(IV)-Ammonnitrat

Zusammenfassung Die Titelverbindung wurde mittels Cer(IV)-Ammonnitrat in Aceton in die cyclischen Ether5 und den Alkohol6 umgewandelt. Mit Methanol als Lösungsmittel wurde das Dimethoxyderivat9 und der Nitratester10 gebildet. Bei Anwesenheit von Olefinen wie etwa Ethylvinylether,DMAD oder Inden wurden keine Cross-Cycloadditionen beobachtet. Hingegen wurde mit Cyclopentadien als Mitreagens eine Mischung vonexo-endo-Diels-Alder-Produkten14 erhalten, wobei das vinylische System von1 als 2-Komponente fungiert. Die Ergebnisse werden mittels eines intermediär auftretenden Radikalkation1 ^·+ als Produkt eines Einelektronentransfers (SET) des neutralen Vorläufers1 zu Ce(IV) rationalisiert.

     

One-step synthesis of tetrahydroindoles by ceric(IV) ammonium nitrate-promoted oxidative cycloaddition of enaminones and vinyl ethers

A new and general one-step procedure to synthesize a variety of biologically interesting tetrahydroindole derivatives was successfully devised by reacting various β-enaminones with vinyl ethers in the presence of ceric(IV) ammonium nitrate as promoter. This novel synthetic method provides a facile and promising strategy to various tetrahydroindole derivatives in moderate to good yields.     

Liquid-Phase and Solventless Oxidation of Cyclohexane,Benzene, and Other Hydrocarbons by Cerium(IV) Catalyzed by Iridium(III) in Acidic Medium

Oxidation of some hydrocarbons dissolved in acetic acid by cerium(IV) sulphate at 100 °C in the presence of traces of iridium(III) chloride (catalyst-substrate 1:56818 to 151515) in the solution phase resulted in good to excellent yields of corresponding carbonyl compounds. In the cases of cyclohexane and benzene, 44% and 51.8% yields of corresponding carbonyl compounds were obtained, whereas in other cases, yield ranged from 34.9 to 99.8%. Yield decreased when reactions were performed in a microwave oven by adsorbing reactants (except acetic acid) on alumina. Decrease in the yield was probably due to the high temperature generated during the course of the reaction, resulting in the loss of organics from evaporation. Conditions were optimized for the highest yields under ambient conditions.     

Ultrasound-assisted one-pot synthesis of 2,4,5-triarylimidazole derivatives catalyzed by ceric (Ⅳ) ammonium nitrate in aqueous media

2,4,5-Triarylimidazoles could be obtained in excellent yields by the one-pot three-component condensation of benzil/benzoin, aldehydes and ammonium acetate in the presence of catalytic amount of the inexpensive,readily available and non-toxic ceric(Ⅳ) ammonium nitrate(CAN) in aqueous media under ultrasound at room temperature.In this reaction the products were obtained in short reaction time and easy operation under mild conditions.     

A new application of cerium(IV) ammonium nitrate [(NH4)2Ce(NO3)3] in fullerene chemistry—free-radical alkoxylation of C60 fullerene on reaction with primary alcohols

The reaction of [60]fullerene with primary aliphatic alcohols (ROH, R = Et, Me, Pr) mediated by cerium(IV) ammonium nitrate [(NH₄)₂Ce(NO₃)₃] affords the corresponding alkoxy-derivatives with a hydroxy group, C₆₀(OR)_x(OH) (x = 3, 4) in high yield. The reaction is characterized by a free radical mechanism confirmed by an EPR study of the alkoxy fullerenyl radical (g = 2.0023).     

Formation of isoxazole derivatives via nitrile oxide using ammonium cerium nitrate (CAN): a novel one-pot synthesis of 3-acetyl- and 3-benzoylisoxazole derivatives

The reactions of alkenes and alkynes with ammonium cerium(IV) nitrate ((NH₄)₂Ce(NO₃)₆, CAN(IV)) in acetone under reflux gave the corresponding 3-acetyl-4,5-dihydroisoxazole and 3-acetylisoxazole derivatives. In the case of acetophenone, 3-benzoyl-4,5-dihydroisoxazole and 3-benzoylisoxazole derivatives were obtained. Reaction of acetone with CAN(IV) afforded the corresponding furoxan (3,4-diacetyl-1,2,5-oxadiazole 2-oxide) as the dimer of nitrile oxide. Moreover, it was found that yields of isoxazole derivatives were improved using ammonium cerium(III) nitrate tetrahydrate ((NH₄)₂Ce(NO₃)₅·4H₂O, CAN(III))-formic acid. The reaction mechanisms based on nitration and formation of nitrile oxide mediated by CAN(IV) or CAN(III) from acetone or acetophenone are also proposed.     

Synthesis and anti-HBV activity of novel 5-substituted pyridin-2(1H)-one derivatives

<正>Four novel 5-substituted pyridine-2(1H)-one derivatives were designed and synthesized by using addition-elimination reactions.The structures of these novelly synthesized compounds were verified by ~1H NMR,ESI-MS and single crystal X-ray diffraction.Furthermore,all four compounds(most notably compound 7a) were found to be highly efficient against hepatitis B virus (HBV) in cultured HepG2 2.2.15 cell,making them promising drug candidates for potential bioactive molecule against hepatitis B.     

Synthesis,characterization, equilibria and biological activity of dimethyltin(IV) complex with 1,4-piperazine

The interaction of dimethyltin(IV) dichloride (DMT) with 1,4-piperazine (PIP) was investigated. The complex formation equilibria of the complexes formed in solution were investigated. The stoichiometry and stability constants of the complexes formed in solution phase were determined at different temperatures and in solutions of dioxane–water mixtures of different dielectric constants. The equilibrium constant for the displacement of piperazine coordinated to dimethyltin(IV) by inosine as a representative of DNA was calculated. (DMT)(PIP)·3H₂O was synthesized and characterized by elemental analysis, spectral, and thermal techniques. The antitumor activity of the complex was screened.     

Studies on the Radical Cyclization of 3‐Oxopropanenitriles and Alkenes with Cerium(IV) Ammonium Nitrate in Ether Solvents

The radical cyclization of 3‐oxopropanenitriles 1a – 1e and alkenes 2a – 2g with cerium(IV) ammonium nitrate (CAN) in ether solvents was investigated (Tables 1 and 2). In the optimization study, 1,3‐dioxolane, 1,4‐dioxane, 1,2‐dimethoxyethane, Et₂O, and THF were used as ether‐based solvents, and the latter was found to be the most effective solvent in radical cyclizations mediated by cerium(IV). This system (cerium(IV)/THF) was applied to cyclizations of various 3‐oxopropanenitriles and 1,3‐dicarbonyl compounds with alkenes resulting in the formation of 4,5‐dihydrofurans in high yields (Table 2 and Scheme 2). The results of the cerium(IV)/THF radical cyclization were compared with those obtained with manganese(III) acetate/AcOH; the cerium(IV)/THF system turned out to be much more efficient.     

Ceric ammonium nitrate (CAN) as a green and highly efficient promoter for the 1,4-addition of thiols and benzeneselenol to α,β-unsaturated ketones

A mild and efficient process for the 1,4-addition of thiols and benzeneselenols to various α,β-unsaturated ketones using a catalytic amount of CAN with excellent product yields is described. This inexpensive, nontoxic, and readily available catalytic ceric(IV) ammonium nitrate system efficiently catalyzes conjugate addition reactions between thiol derivatives and various α,β-unsaturated ketones under solvent-free conditions. A plausible mechanism for the role of CAN, both as a promoter in free radical chain addition reactions as well as a catalyst for the conjugate addition process is proposed.