Lembehsterols A and B,novel sulfated sterols inhibiting thymidine phosphorylase,from the marine sponge Petrosia strongylata

Lembehsterols A (1) and B (2), two novel sulfated sterols, were isolated from the marine sponge Petrosia strongylata. Both sterols showed inhibitory activity against thymidine phosphorylase, which is an enzyme related to angiogenesis in solid tumors. The structures of these sulfated sterols were established on the basis of chemical and physicochemical evidence.     

Controlling the photochemical reactions of alkenes by light-path length effects of a microchannel reactor

Photoirradiation of Me₂CO–H₂O solution of pent-4-en-1-ol (1a) with a high-pressure mercury lamp in a test tube gave 8-hydroxyoctan-2-one (3a) in 66 % yield along with oxetane (4a) and the isomer (4a′) in 10 % yield. Irradiation of the running Me₂CO–H₂O solution of 1a in the flow system of a microchannel reactor (MCR) gave mainly 4a. The photoreaction of 1,1-diphenylethene (2a) with triethylamine gave a Markovnikov-type adduct (5a) and an anti-Markovnikov-type adduct (6a). The use of the MCR enhanced the production of 5a. These phenomena were explained by the light-path length effects of the MCR.     

Comprehensive characterisation of the E phase of 6-octyl-2-phenylazulene

Molecular dynamics in the soft crystal, E phase of 6-octyl-2-phenylazulene was studied by X-ray diffraction, and dielectric and Fourier transform infrared spectroscopies. Clear dielectric dispersion is observed due to the head-to-tail disordering in a kHz range around 400 K. The CH stretching frequencies exhibit more pronounced shifts at the phase transition point from the high-temperature ordered crystal to the E phase than that at the melting from the E phase to the isotropic liquid. The results are discussed in comparison with a typical E series, 4-n-alkyl-4′-isothiocyanatobiphenyl (n being the number of carbon atoms in the alkyl group).     

Asymmetric Aza-Diels–Alder Reaction with Ion-Paired—Iron Lewis Acid—Brønsted Acid Catalyst

The development and use of a multiple-activation catalyst with ion-paired Lewis acid and Brønsted acid in an asymmetric aza-Diels–Alder reaction of simple dienes (non-Danishefsky-type electron-rich dienes) was achieved by utilizing the [FeBr₂]⁺[FeBr₄]⁻ combination prepared in situ from FeBr₃ and chiral phosphoric acid. Synergistic effects of the highly active ion-paired Lewis acid [FeBr₂]⁺[FeBr₄]⁻ and a chiral Brønsted acid are important for promoting the reaction with high turnover frequency and high enantioselectivity. The multiple-activation catalyst system was confirmed using synchrotron-based X-ray absorption fine structure measurements, and theoretical studies. This study reveals that the developed catalyst promoted the reaction not only by the interaction offered by the ion-paired Lewis acid and the Brønsted acid but also noncovalent interactions.     

High pressure vapor–liquid equilibria for carbon dioxide + tetrahydrofuran mixtures

Vapor–liquid equilibria and saturated density for carbon dioxide + tetrahydrofuran mixtures at high pressures were measured by the analytical method at the temperatures 298.15 and 313.15 K. The experimental apparatus equipped with three Anton Paar DMA 512S vibrating tube density meters was previously developed for measuring vapor–liquid–liquid equilibrium at high pressures. The equilibrium composition and saturated density of each phase were determined by gas chromatograph and vibrating tube density meters, respectively. The bubble point pressure at the temperature 313.15 K was further measured by the synthetic method. The experimental data were correlated with Soave–Redlich–Kwong (SRK) equation of state and the pseudocubic equation of state.     

Self-assembly of flexible supramolecular metallacyclic ensembles: structures and adsorption properties of their nanoporous crystalline frameworks

The syntheses, structures, and N2 adsorption properties of six new supramolecular metallacycles are reported. Flexible ditopic linkers, 1-4, with systematically varied lengths and conformational degrees of freedom were synthesized utilizing ester linkages. They were used in combination with (dppp)M(OTf)2, where M = Pt(II) and Pd(II), and cis-(Me3P)2Pt(OTf)2 to form flexible supramolecular metallacycles 5-10 in 88-98% isolated yields. Their structures were characterized via multinuclear NMR and X-ray crystallography. The metallacycles stack to form porous structures in the crystalline state. The pore dimensions depend on both the phosphorus ligands attached to the metals and the flexible linkers. Adsorption studies on the porous materials show that 5a, 6, 8, and 9 held 11.7, 16.5, 5.7, and 6.8 cm3/g STP of N2 at 77 K, respectively. A guest-exchange study with nitromethane and toluene reveals that the nanopore in 5 is flexible, a property which was transferred from the linker to the supramolecular structure in the solid state.     

Organotrichlorogermane synthesis by the reaction of elemental germanium, tetrachlorogermane and organic chloride via dichlorogermylene intermediate

Organotrichlorogermanes were synthesized by the reaction of elemental germanium, tetrachlorogermane and organic chlorides, methyl, propyl, isopropyl and allyl chlorides. Dichlorogermylene formed by the reaction of elemental germanium with tetrachlorogermane was the reaction intermediate, which was inserted into the carbon-chlorine bond of the organic chloride to give organotrichlorogermane. When isopropyl or allyl chloride was used as an organic chloride, organotrichlorogermane was formed also in the absence of tetrachlorogermane. These chlorides were converted to hydrogen chloride, which subsequently reacted with elemental germanium to give the dichlorogermylene intermediate. The reaction of elemental germanium, tetrachlorogermane and organic chlorides provides a simple and easy method for synthesizing organotrichlorogermanes, and all the raw materials are easily available.     

Distributed computing and NMR constraint-based high-resolution structure determination: applied for bioactive Peptide endothelin-1 to determine C-terminal folding

Distributed computing has been implemented to the solution structure determination of endothelin-1 to evaluate efficiency of the method for NMR constraint-based structure calculations. A key target of the investigation was determination of the C-terminal folding of the peptide, which had been dispersed in previous studies of NMR, despite its pharmacological significances. With use of tens of thousands of random initial structures to explore the conformational space comprehensively, we determined high-resolution structures with good convergences of C-terminal as well as previously defined N-terminal structures. The previous studies had missed the C-terminal convergence because of initial structure dependencies trapped in localized folding of the N-terminal region, which are strongly constricted by two disulfide bonds.