Enantiodifferentiating [2+2] photocycloaddition of cyclohexenone carboxylic acid with ethylene using 8-phenylmenthyl amine as a chiral template

Enantiodifferentiating [2+2] photocycloaddition of cyclohexenone carboxylic acid with the smallest olefin, ethylene, was accomplished using 8-phenylmenthyl amine as a chiral template. Particularly, we succeeded in enhancing the enantiomeric excess (ee) value by selective excitation of a chiral substrate–template supramolecular complex.     

Rhodium-catalyzed anti-Markovnikov intermolecular hydroalkoxylation of terminal acetylenes

We report here the first transition-metal-catalyzed anti-Markovnikov intermolecular hydroalkoxylation of terminal acetylenes to give enol ethers in high yields without using bases. Arylacetylenes as well as alkenyl- and alkylacetylenes were coupled with aliphatic alcohols, and the products were obtained with high Z selectivity in most cases. Effective catalysts were 8-quinolinolato rhodium complexes, which are structurally simple but have been relatively unexplored as catalysts.     

Direct Synthesis of Benzofuro[2,3‐b]pyrroles through a Radical Addition/[3,3]‐Sigmatropic Rearrangement/Cyclization/Lactamization Cascade

A straightforward synthetic method for the construction of benzofuro[2,3‐b]pyrrol‐2‐ones by a novel domino reaction through a radical addition/[3,3]‐sigmatropic rearrangement/cyclization/lactamization cascade has been developed. The domino reaction of O‐phenyl‐conjugated oxime ether with an alkyl radical allows the construction of two heterocycles with three stereogenic centers as a result of the formation of two C?C bonds, a C?O bond, and a C?N bond in a single operation, leading to pyrrolidine‐fused dihydrobenzofurans, which are not easily accessible by existing synthetic methods. Furthermore, asymmetric synthesis of benzofuro[2,3‐b]pyrrol‐2‐one derivatives through a diastereoselective radical addition reaction to a chiral oxime ether was also developed.     

Construction and evaluation of a miniature electron ion coincidence analyzer mounted on a conflat flange with an outer diameter of 114 mm.

We have developed a miniature electron ion coincidence (EICO) analyzer mounted on a conflat flange with an outer diameter of 114 mm. It consists of a cylindrical mirror analyzer (CMA), a time-of-flight ion mass spectrometer (TOF-MS), a commercially available linear motion feed through, and a tilt adjustment mechanism. Each sample surface was irradiated by synchrotron radiation, and the energies of emitted electrons were analyzed and detected by the CMA, while desorbed ions were collected by the TOF-MS in coincidence with the electrons. The performance of the EICO analyzer was tested by measuring the Auger-electron H+ photoion coincidence spectrum of condensed water at 4a1 <-- O 1s resonance.     

Chemical speciation of radionuclides through the microbial process in soils

Environmental factors (nutrients and pH) influence the retention of Sr, Cs, and Ba as analogue of long-lived radionuclides by the microorganism. The effect of pH and concentration of organic nutrients are proved to be significant factors for retention of cations (Sr, Cs and Ba) by the microorganisms inoculated from surface soil. Microorganisms can affect the speciation of Sr, Cs, and Ba in the environment. Concentration of organic nutrients and pH are indicated to be the important environmental factors in the consideration of the migration of the radionuclides through microbial processes in the terrestrial environment.     

Qualitative and quantitative analysis of Swertia herbs by high performance liquid chromatography-diode array detector-mass spectrometry (HPLC-DAD-MS)

We evaluated the composition of Swertia herbs using high performance liquid chromatography-diode array detector-mass spectrometry (HPLC-DAD-MS). Eleven peaks of 6 species were unequivocally identified by comparing their retention times, UV spectra, on-line electrospray ionization mass (ESI-MS) spectra, and collision-induced dissociation mass spectrometry/mass spectrometry (CID-MS/MS) data with those of authentic compounds. We adopted wavelengths of 254 nm, 340 nm and 230 nm to simultaneously determine these 11 compounds. By comparing the overall DAD and total ion current (TIC) profiles of various samples, the 6 species were differentiated in terms of the occurrence and/or relative concentrations of the eleven compounds. Our novel validated HPLC-DAD-MS method not only facilitates quality control and identification of Swertia herbs, but is also applicable to systematic investigations of the distribution of secoiridoids, flavonoids, and xanthones in the genus Swertia.     

Carbon–Carbon Bond Formation via Catalytically Generated Aminocarbene Complexes: Rhodium-Catalyzed Hydroaminative Cyclization of Enynes with Secondary Amines

We report a hydroaminative cyclization of enynes using phosphine-quinolinolato rhodium catalysts. The hydroaminative cyclization of 2-vinylphenylacetylene derivatives with secondary amines gives 2-aminoindenes in good yields. The reaction is considered to proceed through carbon–carbon bond formation on a catalytically generated aminocarbene ligand.     

An atomically controlled Si film formation process at low temperatures using atmospheric-pressure VHF plasma

To grow epitaxial Si films with atomic- and electronic-level perfection, a high-temperature chemical vapor deposition (CVD) process (>1000 °C) has been generally employed. To reduce the growth temperature below 600?°C but keeping a high deposition rate, other energy sources than thermal heating are required. Atmospheric pressure plasma CVD (AP-PCVD) is considered to be suitable for fabricating high-quality films at high deposition rates due both to the high radical density and to the low ion bombardment against the film surface, because the collision frequency among ions and neutral atoms is high. The present study focuses on the low-temperature growth of epitaxial Si, and experimentally demonstrates that AP-PCVD is capable of growing epitaxial Si films with high perfection applicable for semiconductor devices. It is found that the pre-growth cleaning of the Si surface by H(2) AP plasma is effective to grow high-purity Si films, and that the exposure of a film-growing surface to AP plasma during growth is important to form particle-free and defect-free Si films. From the experimental results and the first-principles molecular dynamics simulations of surface atomic reactions, it can be mentioned that both H atoms in the AP plasma and high-density He atoms having thermal kinetic energy contribute to the reduction of growth temperature by supplying considerable energy to the surface.     

Benzyl radical addition reaction through the homolytic cleavage of a benzylic C-H bond

Direct generation of a benzyl radical by C-H bond activation of toluenes and the addition reaction of the resulting radical to an electron deficient olefin were developed. The reaction of dimethyl fumarate with toluene in the presence of Et(3)B as a radical initiator at reflux afforded 2-benzylsuccinic acid dimethyl ester in good yield.