Snapshot of the palladium(II)-catalyzed oxidative biaryl bond formation by X-ray analysis of the intermediate diaryl palladium(II) complex

Pd(II) caught in the act: The diaryl Pd(II) intermediate of a Pd(II)-catalyzed oxidative biaryl bond formation proceeding via a double C-H bond activation has been isolated and fully characterized, including an X-ray crystal structure analysis. Stabilization due to chelation by adjacent pivaloyloxy and acetyl groups has allowed the isolation of this long-sought crucial intermediate. On gentle warming, the complex is transformed into a carbazole product, and the catalytically active Pd(II) species is regenerated by oxidation with Cu(II).     

Stereoselective synthesis and hormonal activity of novel dafachronic acids and naturally occurring steroids isolated from corals

A stereoselective synthesis of (25S)-Δ(1)-, (25S)-Δ(1,4)-, (25S)-Δ(1,7)-, (25S)-Δ(8(14))-, (25S)-Δ(4,6,8(14))-dafachronic acid, methyl (25S)-Δ(1,4)-dafachronate and (25S)-5α-hydroxy-3,6-dioxocholest-7-en-26-oic acid is described. (25S)-Δ(1,4)-Dafachronic acid and its methyl ester are natural products isolated from corals and have been obtained by synthesis for the first time. (25S)-5α-Hydroxy-3,6-dioxocholest-7-en-26-oic acid represents a promising synthetic precursor for cytotoxic marine steroids.     

Reactions of 1-alkyl-1,2-diphospholes with 1,3-dipoles: diphenyldiazomethane and nitrones

The reaction of 1-alkyl-1,2-diphosphacyclopenta-2,4-dienes (1-alkyl-1,2-diphospholes) (1) with diphenyldiazomethane proceeds at room temperature via unstable [3+2] cycloadducts to form bicyclic phosphiranes (2). However, 1-alkyl-1,2-diphospholes (1) react with N,alpha-diphenylnitrone or N-tert-butyl-alpha-phenylnitrone depending on the temperature to give either dimers of 1-alkyl-1-oxo-1,2-diphospholes (5) or 1-alkyl-1,7-dioxo-6-azo-1,7-diphospha-bicyclo[3.2.0]hept-2-enes (7) - phosphorus analogues of β-lactams.     

Crystal and Molecular Structure of Acylalmino Derivatives of 1-(2,4,6-Trichlorophenyl)-4,5-dihydropyrazol-5-one

The structure of acylamino derivatives of 1-(2,4,6-trichlorophenyl)-4,5-dihydropyrazol-5-one was studied by X-ray diffraction. 3-Acetylamino-1-(2,4,6-trichlorophenyl)-4,5-dihydropyrazol-5-one and 3-benzoylamino-1-(2,4,6-trichlorophenyl)-4,5-dihydropyrazol-5-one exist in crystal as CH tautomers. The nature and number of acylamino groups were found to affect the nature of intermolecular hydrogen bonds in the crystals studied.     

Molecular structure of eight-membered cyclic sulfites with two planar fragments

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2033–2036, September, 1988.     

Optical properties of cadmium sulfide nanoparticles on the surface of polytetrafluoroethylene nanogranules

The spectral characteristics in the visible range of synthesized nanocomposites based on cadmium sulfide and ultradispersed polytetrafluoroethylene are investigated experimentally. Local perturbations are found in the long-wavelength regions of the reflection and absorption spectra, which are related to the optical transitions between the critical points of the valence and conduction bands of the nanocomposite. The dispersion relations for the refractive index and the absorption coefficient are obtained for undoped and managanesedoped nanocomposites. The following important parameters of the nanocomposites are obtained from the spectral measurements: the fundamental optical absorption edge (the band gap), the refractive index (ω → 0), and the absorption coefficient. It is shown that doping with managanese affects changes in these parameters.