Copper(I) iodide-catalysed arylation of acetoacetate to yield 2-arylacetic acid esters

The C-C coupling reaction between ethyl acetoacetate and aryl halides in the presence of CuI is described. The effects of solvent, ligands such as vicinal diamines and amino acids, base and temperature are reported. The arylated acetoacetate ester is deacylated under the reaction conditions resulting in the generation of 2-arylacetic acid esters, constituting a mild alternative to direct arylation of carboxylate esters.     

Pd-catalyzed reduction of aryl halides using dimethylformamide as the hydride source

The Pd-catalyzed homocoupling of aryl halides in a basic DMF solution is often accompanied by the dehalogenation of the substrate as side reaction. When an inorganic base such as sodium bicarbonate is used, the reducing role of the solvent has been demonstrated using DMF-d₇ and GC/MS analysis.     

Iodine catalyzed efficient synthesis of symmetrical diaryl sulfoxides from arenes and thionyl chloride under solvent-free conditions

Synthesis of symmetrical diaryl sulfoxides from arenes and thionyl chloride in the presence of a catalytic amount of iodine at room temperature under solvent-free conditions is described.Mild reaction conditions,easy workup,high yield,and easily available catalyst are important features of this method.     

Synthesis of new pyrrolo-[3,4-c]isoxazole, pyrrolo[2,3-d]-[1,2,3]triazole, triazolo[4,5-c]-pyridazine, and dipyrrolo-[3,2-b:3′,4′-d]pyran derivatives

New pyrrolo[3,4-c]isoxazole derivatives were synthesized from the key intermediates 4-cyanopyrrolidin-3-ones in two steps. Pyrrolo[2,3-d][1,2,3]triazoles and triazolo[4,5-c]pyridazine were obtained from 2-arylhydrazono-4-cyano-1-(4′-methoxyphenyl)-3-oxopyrrolidines by refluxing with phenylhydrazine in either ethanol or glacial acetic acid. Aldol self-condensation of 1-aryl-4-cyanopyrrolidin-3-ones afforded dipyrrolo-[3,2-b:3′, 4′-d]pyran derivatives. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1841–1848, December, 2007.     

Thin‐Film Infrared Spectroscopy of Acetonitrile

Acetonitrile and [D₃]acetonitrile in the vicinal region of a planar AgX fiber contain linear dipole–dipole linked oligomers as shown by 1) comparison of infrared band intensity ratios in the gaseous and condensed phases and 2) remarkable plots of absorbance (C? N stretch) versus time during evaporation from an AgX planar fiber element. The plots (CH₃CN 2252 cm^?1, CD₃CN 2262 cm^?1) reveal the presence of octamers, hexamers, tetramers, and dimers along with some heptamer, trimer, and monomer structures. A novel isotope effect arises from the somewhat smaller size of the CD₃CN resulting in an increase in the CN band intensity. The organized oligomers may be termed pseudocrystals and are the main components responsible for absorption intensity in the infrared spectrum of acetonitrile, on the AgX planar fiber or in an IR cell.     

Vibrational dynamics of hydrogen‐bonded HCN complexes with OH and NH acids: Computational DFT systematic study

Vibrational properties (band position, infrared [IR], and Raman intensities) of C?N stretching mode were studied in 65 gas phase hydrogen‐bonded 1:1 complexes of HCN with OH acids and NH acids using density functional theory (DFT) calculations at the B3LYP‐6‐311++G(d,p) level. Furthermore, general characteristics of the hydrogen bonds and vibrational changes in acids OH/NH stretching bands were also considered. Experimentally observed blue shift of the C?N stretching band promoted by hydrogen bonding, which shortens the triple bond length, is very well reproduced and quantitatively depends on the hydrogen bond length. Both IR and Raman ν(C?N) band intensities are enhanced, also in good agreement with the experimental results. IR intensity increase is a direct function of the hydrogen bond energy. However, the predicted Raman intensity raise is a more complex function, depending simultaneously on characteristics of both the hydrogen bond (C?N bond length) and the H‐donating acid (polarizability). With these two parameters, ν (C?N) Raman intensities of the complexes are explained with a mean error of ±2.4%. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

果胶负载钯催化剂的制备及Suzuki反应催化性能

以柑橘皮果胶为载体,采用吸附法制备了果胶负载钯催化剂,并将其应用于四苯硼钠与溴代芳烃的交叉偶联反应中.该反应体系以聚乙二醇400(PEG 400)/H2O为反应溶剂,三乙胺为碱,在空气中于110℃反应15~60 min,四苯硼钠中4个苯基均可顺利参与反应,高产率地获得相应的目标化合物.该方法具有条件温和、反应时间短、收率高且催化剂可循环利用等优点.     

A polystyrene-supported triflating reagent for the synthesis of aryl triflates

An insoluble polystyrene-supported triflating reagent has been prepared by suspension co-polymerization of N-(4-vinylphenyl)trifluoromethanesulphonimide, styrene and the JandaJel^® cross-linker. This reagent, in the presence of triethylamine, allows for the efficient synthesis of aryl triflates from a wide range of phenols in a process that permits the desired product to be isolated from the reaction mixture in essentially pure form via several filtration and concentration operations. Adding to the utility of this reagent is its ability to be easily recovered, regenerated and reused. Both soluble and insoluble bifunctional polymers containing trialkylamine moieties in addition to triflimide groups were also prepared and examined as triflating reagents. Unfortunately these reagents afforded only modest yields of the desired products in representative reactions.     

Synthetic applications of aryl radical building blocks for cyclisation onto azoles

2-(2-Bromophenyl)ethyl groups have been used as building blocks in radical cyclisation reactions onto azoles to synthesise tri- and tetra-cyclic heterocycles. 2-(2-Bromophenyl)ethyl methanesulfonate was used to alkylate azoles (imidazoles, pyrroles, indoles and pyrazoles) for the synthesis of the radical precursors. Cyclisations of the intermediate aryl radicals yield new 6-membered rings attached to the azoles. The aryl radicals undergo intramolecular homolytic aromatic substitution onto the azole rings. Tributylgermanium hydride has been used with success to replace the toxic and troublesome tributyltin hydride. Initial studies show that the protocol can be used on solid phase resins. The molecular and crystal structures of methyl 5,6-dihydroimidazo[5,1-a]iso-quinoline-1-carboxylate and methyl 5,6-dihydroimidazo[2,1-a]isoquinoline-3-carboxylate were determined by X-ray crystallography.     

An efficient Stille cross-coupling reaction catalyzed by Pd(OAc)2/DAB-Cy catalytic system

An efficient palladium-catalyzed Stille cross-coupling reaction has been developed. In the presence of 3 mol% of Pd(dba)₂ and 6 mol% of DAB-Cy (1,4-dicyclohexyl-diazabutadiene), various aryl halides (iodides and bromides) were coupled with organotin compounds to afford the corresponding biaryls and alkyne in good to excellent yields. Furthermore, high TONs [turnover numbers, TONs up to 950,000 for the reaction of 1-iodo-4-nitrobenzene and tributyl(phenyl)stannane] for the Stille cross-coupling reaction were observed.