Ritter-type iodo(iii)amidation of unactivated alkynes for the stereoselective synthesis of multisubstituted enamides

The Ritter reaction, Brønsted- or Lewis acid-mediated amidation of alkene or alcohol with nitrile via a carbocation, represents a classical method for the synthesis of tertiary amides. Although analogous reactions through a vinyl cation or a species alike may offer a route to enamide, an important synthetic building block as well as a common functionality in bioactive compounds, such transformations remain largely elusive. Herein, we report a Ritter-type trans-difunctionalization of alkynes with a trivalent iodine electrophile and nitrile, which affords β-iodanyl enamides in moderate to good yields. Mediated by benziodoxole triflate (BXT), the reaction proves applicable to a variety of internal alkynes as well as to various alkyl- and arylnitriles. The benziodoxole group in the product serves as a versatile handle for further transformations, thus allowing for the preparation of various tri- and tetrasubstituted enamides that are not readily accessible by other means.

Ritter-type trans-selective iodo(iii)amidation of internal alkynes with benziodoxole triflate and various nitriles has been achieved for the stereocontrolled synthesis of multisubstituted enamides.     

Electromagnetic cross sections of double giant dipole resonances in 136Xe and 208Pb within the phonon damping model

The electromagnetic cross sections of the double giant dipole resonances (DGDR) in 136Xe and 208Pb are calculated using the strength functions obtained within the phonon damping model. The parameters of the model have been selected to describe reasonably well the single giant dipole resonance in these nuclei. The results are found in an overall agreement with the recent experimental data for the DGDR cross sections in exclusive measurements at near-relativistic energies.     

Magnetic hyperfine structure of muonic and electronic atoms

The magnetic hyperfine structure of atoms is studied. A new compact expression is introduced for the magnetic hyperfine anomaly. A theoretical foundation is given for an empirical formula discovered by Moskowitz and Lombardi. The effects of core polarization and mesonic exchange currents are discussed. There are two kinds of core polarization, Δl = 0 and Δl = 2. The latter is shown to be important to explain certain isotope shifts, though it is smaller than the former Δl = 0 effect.     

Enantioselective allylic substitution of cinnamyl esters catalyzed by iridium-chiral aryl phosphite complex: conspicuous change in the mechanistic spectrum by a countercation and solvent

Iridium-catalyzed asymmetric allylic alkylation of monoaryl substrates 4-6 with chiral phosphites 1-3 has been investigated. Although branched isomers were formed with high regioselectivities, the enantioselectivities of these products were remarkably influenced by solvents, countercations, and additives (ZnCl(2) and LiCl).     

Pressure-induced sharp coordination change in liquid germanate

Local structures around germanium in liquid germanate have been investigated by means of in situ x-ray absorption measurements up to 9 GPa at 1273 K. Liquid germanate consisting of tetrahedrally coordinated germanium contracts with increasing pressure without significant changes in the local structure up to 2.5 GPa and then shows an abrupt fourfold-to-sixfold coordination change around 3 GPa. The coordination change is completed below 4 GPa where upon a high-density liquid consisting of octahedrally coordinated germanium becomes stable. The GeO6 octahedron in the high-density liquid is more compressible than that in solids.     

Charge/orbital ordering structure of Pr(1-x)Ca(x)MnO(3)(x = 3/8) examined by low-temperature transmission electron microscopy

The structural phase transition of Pr(1-x)Ca(x)MnO(3)(x = 3/8) was investigated by means of low-temperature transmission electron microscopy. Superlattice reflection spots with a modulation wave vector q(1) = (0,1/2,0) appeared below 230 K, indicating formation of the d(3x(2-r(2))/d(3y(2)-r(2)) type of charge/orbital ordering. Below 150 K, a new series of superlattice reflection spots with a modulation wave vector q(2) = (1/4,1/4,1/2) appeared, suggesting an additional ordering of excess 1/8 Mn(3+), necessary due to the deviation of x from 1/2, with the occupation of the d(3z(2-r(2)) type of e(g) orbital.     

Prolonged Plasma Levels of Ketoprofen after Oral Administration of Its α-Cyclodextrin Conjugate/Ethylcellulose Dispersion in Rats

6^A-O-[2-(3-benzoylphenyl)propinoyl]--cyclodextrin (KP/-CyD conjugate), in which an anti-inflammatory drug, ketoprofen (KP), is covalently bound to one of the primary hydroxyl groups of -cyclodextrin, was prepared, and the CyD conjugate-based prolonged-release system was designed by combining the KP/-CyD conjugate (used as a delayed-release fraction) with the KP/ethylcellulose (EC) solid dispersion (used as a slow-release fraction). The conjugate showed a typical delayed-release pattern after oral administration to rats, i.e., plasma levels of KP increased after a lag time of about 3 h and reached a maximum concentration at about 9 h. The co-administration of the conjugate and the EC solid dispersion gave a sustained-release pattern of KP, i.e., a constant plasma KP level was maintained for at least 24 h. The long circulating release patterns in plasma KP levels after oral administration were reflected in the anti-inflammatory effect using with carrageenan-induced acute edema in rat paw.     

Deuteron-induced activation cross-sections on natural copper up to 24 MeV

Activation cross-sections of ^natCu(d,x)^62,65Zn,⁶⁴Cu,^60g+mCo,⁵⁹Fe reactions were measured using a stacked foil activation technique combined with HPGe gamma-ray spectrometry up to the deuteron energy of 24 MeV. Measured data were critically compared with the available literature data and theoretical data extracted from the TENDL-2012 library, and found only partial agreements among them. Cross-sections of ^natCu(d,x)⁵⁹Fe reactions are reported here for the first time in the energy region of 19–23 MeV. Measured cross-sections of the long-lived ⁶⁵Zn, ^60gCo and ⁵⁹Fe radionuclides are significant for understanding the activation behaviour of copper, an essential structural material used in accelerator and nuclear industry.     

Displacement-type ferroelectricity with off-center magnetic ions in perovskite Sr(1-x)Ba(x)MnO3

We report a ferroelectric transition driven by the off-centering of magnetic Mn(4+) ions in antiferromagnetic Mott insulators Sr(1-x)Ba(x)MnO(3) with a perovskite structure. As x increases, the perovskite lattice shows the typical soft-mode dynamics, as revealed by the momentum-resolved inelastic x-ray scattering and far-infrared spectroscopy, and the ferroelectricity shows up for x ≥ 0.45. The observed polarization is comparable to that for a prototypical ferroelectric BaTiO(3). We further demonstrate that the magnetic order suppresses the ferroelectric lattice dilation by ～70% and increases the soft-phonon energy by ～50%, indicating the largest magnetoelectric effects yet attained.