Metallaphotoredox Difluoromethylation of Aryl Bromides

Herein, we report a convenient and broadly applicable strategy for the difluoromethylation of aryl bromides by metallaphotoredox catalysis. Bromodifluoromethane, a simple and commercially available alkyl halide, is harnessed as an effective source of difluoromethyl radical by silyl‐radical‐mediated halogen abstraction. The merger of this fluoroalkyl electrophile activation pathway with a dual nickel/photoredox catalytic platform enables the difluoromethylation of a diverse array of aryl and heteroaryl bromides under mild conditions. The utility of this procedure is showcased in the late‐stage functionalization of several drug analogues.     

Generation of Aryl(2‐lithiophenyl)methanone O‐Methyl Oximes and Their Use for the Synthesis of N‐(3‐Alkyl‐1‐aryl‐ or 1,3‐diaryl‐1H‐isoindol‐1‐yl)‐O‐methylhydroxylamines via the Reaction with Nitriles

An efficient two‐step procedure for the preparation of a new type of 1H‐isoindoles, i.e., N‐(3‐alkyl‐1‐aryl‐ or 1,3‐diaryl‐1H‐isoindol‐1‐yl)‐O‐methylhydroxylamines 5 , from readily available aryl(2‐bromophenyl)methanones 1 has been developed. Aryl(2‐bromophenyl)methanone O‐methyloximes 2 , derived from the corresponding ketones, were treated with BuLi in Et₂O at 0° to generate novel lithium compounds, aryl(2‐lithiophenyl)methanone O‐methyloximes 3 , which were allowed to react with nitriles to give the desired products 5 in moderate‐to‐fair yields.     

Pressure-induced superconductivity in beta- Na (0.33) V(2)O(5) beyond charge ordering

We report the discovery of a new superconducting phase in highly correlated 3d electron systems. The compound is beta-vanadium bronze, beta- Na0.33V 2O5, in which the charge-ordered phase collapses under hydrostatic high pressure and a pressure-induced superconducting phase appears around T(S C)=8 K, P=8 GPa. This report presents the first observation not only of superconductivity in vanadium oxides but also of a phase transition from charge ordered to superconducting on a pressure-temperature (P- T) plane. The phase diagrams seem to have universal aspects across the classes of materials. This indicates a profound physics of superconductivity in highly correlated electron systems.     

Transition curves for the variance of the nearest neighbor spacing distribution for Poisson to Gaussian orthogonal and unitary ensemble transitions

Using an appropriate 2x2 random matrix ensemble, transition curves for the variance of the nearest neighbor spacing distribution are constructed for the Poisson to Gaussian orthogonal and unitary ensemble transitions in terms of an easily identifiable transition parameter.     

Propagating beam analysis of fiber wavelength filters with a depressed-index section

A wavelength filter consisting of single-mode and few-mode fibers is investigated numerically. A simple finite-difference beam-propagation method, in which a transparent boundary condition can be imposed, is developed for circularly symmetric waveguides. After confirming the validity of the numerical method by the mode-mismatch loss, we calculate the propagating field in the fiber wavelength filter, in which interference between LP₀₁, and LP₀₂ modes occurs. To improve the filtering operation, a depressed-index fiber is employed for the few-mode fiber. The effects of the radius and refractive index of the depressed section on the transmission power are revealed and discussed. Power is suppressed to less than 0.1% at 1.3 μm, while maintaining power transmission of more than 85% at 1.55 μm. It is also found that the filtering operation shifts to higher wavelengths as the input power is increased when we choose a self-focusing nonlinear material in the depressed section.     

Synthesis of novel liquid crystals having the perfluoropyrrolidino group

Novel liquid crystals which have the perfluoropyrrolidino group, a heterocyclic perfluoroalkyl group, and which show smectic phases have been synthesized with perfluoro-(2-pyrrolidinopropionyl fluoride) as one of the starting materials. Analogues with a polymerizable functional group also have been prepared and polymerized to give side chain liquid crystal polymers.     

Determination of inorganic arsenic and organic arsenic compounds in marine organisms by hydride generation/cold trap/gas chromatography— mass spectrometry

The behavior of arsenite, methylarsonic acid, dimethylarsinic acid, trimethylarsine oxide, dimethyl-R-arsine oxides, and trimethyl-R-arsonium compounds (R = carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl) toward sodium borohydride and hot aqueous sodium hydroxide was investigated. The arsines obtained by sodium borohydride reduction of the undigested and digested solutions were collected in a liquid-nitrogen cooled trap, separated with a gas chromatograph, and detected with a mass spectrometer in the selected-ion-monitoring mode. The investigated arsenic compounds were stable in hot 2 mol dm^?3 sodium hydroxide except arsenobetaine [trimethyl(carboxymethyl)arsonium zwitterion] that was converted to trimethylarsine oxide, and dimethyl(ribosyl)arsine oxides that were decomposed to dimethylarsinic acid. Hydride generation before and after digestion of extracts from marine organisms allowed inorganic arsenic, methylated arsenic, arsenobetaine, and ribosyl arsenic compounds to be identified and quantified. This method was applied to extracts from shellfish, fish, crustaceans, and seaweeds.