Catalytic asymmetric allylation of 3,4-dihydroisoquinolines and its application to the synthesis of isoquinoline alkaloids

A catalytic asymmetric allylation of 3,4-dihydroisoquinoline was carried out with allyltrimethoxylsilane-Cu as the nucleophile in the presence of DTBM-SEGPHOS as the chiral ligand to afford corresponding chiral 1-allyltetrahydroisoquinoline derivatives in good yield and stereoselectivity. The allyl adduct thus obtained was applied to the synthesis of several isoquinoline alkaloids such as crispine A and homolaudanosine. The reaction was further used for the synthesis of the isoquinoline moiety of schulzeine A.     

Formation and dielectric properties of anodic oxide films on Zr–Al alloys

Zr–Al alloys containing up to 26 at.% aluminum, prepared by magnetron sputtering, have been anodized in 0.1 mol dm⁻³ ammonium pentaborate electrolyte, and the structure and dielectric properties of the resultant anodic oxide films have been examined by grazing incidence X-ray diffraction, transmission electron microscopy, Rutherford backscattering spectroscopy, and AC impedance spectroscopy. The anodic oxide film formed on zirconium consists of monoclinic and tetragonal ZrO₂ with the former being a major phase. Two-layered anodic oxide films, comprising an outer thin amorphous layer and an inner main layer of crystalline tetragonal ZrO₂ phase, are formed on the Zr–Al alloys containing 5 to 16 at.% aluminum. Further increase in the aluminum content to 26 at.% results in the formation of amorphous oxide layer throughout the thickness. The anodic oxide films become thin with increasing aluminum content, while the relative permittivity of anodic oxide shows a maximum at the aluminum content of 11 at.%. Due to major contribution of permittivity enhancement, the maximum capacitance of the anodic oxide films is obtained on the Zr–11 at.% Al alloy, being 1.7 times than on zirconium at the formation voltage of 100 V.     

Potential of Hibiscus sabdariffa L. and Hibiscus Acid to Reverse Skin Aging

Hibiscus sabdariffa L. (HS) has a long history of edible and medicinal uses. In this study, the biological activities of the extracts, chromatographic fractions, and hibiscus acid obtained from HS were evaluated for their potential bioactivities. Their ability to promote extracellular matrix synthesis in skin fibroblasts was evaluated by enzyme-linked immunosorbent assays. Their anti-inflammatory activity was evaluated in a nitric oxide (NO)–Griess inflammatory experiment. Furthermore, hibiscus acid was found to have a strong anti-oxidative stress effect through the establishment of an oxidative stress model induced by hydrogen peroxide. Several assays indicated that hibiscus acid treatment can effectively reduce extracellular adenosine triphosphate (ATP) secretion and carbonyl protein production, as well as maintain a high level of reduced/oxidized glutathione (GSH/GSSG) in skin cells, thus providing a possible mechanism by which hibiscus acid can counter antioxidative stress. The present study is the first to explore the reversing skin aging potential and the contributory component of HS.     

Activation of Dihydrogen by Masked Doubly Bonded Aluminum Species

Activation of dihydrogen by masked dialumenes (Al=Al doubly bonded species) is reported. Reactions of barrelene‐type dialumanes, which have the reactivity as masked equivalents of 1,2‐diaryldialumenes ArAl=AlAr, with H₂ afforded dihydroalumanes ArAlH₂ at room temperature (Ar: bulky aryl groups). These dihydroalumanes form hydrogen‐bridged dimers [ArHAl(μ‐H)]₂ in the crystalline state, while a monomer–dimer equilibrium was suggested in solution. The 1,2‐diaryldialumenes generated from the barrelene‐type dialumanes are the putative active species in the cleavage of H₂.     

Single-electron-capture cross sections for 0.4–5.0 keV He+ ions incident on alkali-vapor targets

Total cross sections for single-electron capture by He⁺ ions in vapor targets of Cs, Rb, K and Na have been determined in the energy range 0.4–5.0 keV. The energy dependence of the cross-section curves is very similar for all the targets. The cross sections for all the targets are maximum at about the same energy, 1.5 keV. Comparison is made with other reported experimental and theoretical results.     

Totalsynthetische untersuchungen an steroiden—VIII Einführung der C-substituenten in die angulare stellung der kondensierten ringsysteme (teil 3). Einwirkung von kaliumcyanid unter zusatz von ammoniumchlorid auf rac. D-homo-18-nor-androstanderivate

Durch Einwirkung von 2 Mol Kaliumcyanid und 1·75 Mol Ammoniumchlorid und nachträgliche Ketalisierung und Acetylierung liess sich rac. -Homo-18-nor-13(17a)-androstan-3β-ol-17-on (I) in die verschiedenen am C₁₃ cyanierten Verbindungen verwandeln. Das Bildungsverhältnis von 13β- zur 13-Cyanverbindung lag bei 5:3. Die räumlichen Strukturen aller hierbei erhaltenen Verbindungen wurden ermittelt. Die angeführten Reaktionsfolgen stellen eine neue Methode zur Einführung der angularen Substituenten dar und lieferten einen Anhaltspunkt zur Totalsynthese der normalen sowie der in 18-Stellung mit einer funktionellen Gruppe versehenen Steroide.     

Synthetic studies on β-lactam antibiotics. VII. Mild removal of the benzyl ester protecting group with aluminum trichloride

The benzyl ester protecting group in β-lactam derivatives can be cleanly removed by treatment with aluminum trichloride under mild conditions, preferably in the presence of anisole, to give the corresponding free acids in high yields.     

Synthetic studies on β-lactam antibiotics. 15. conversion of 7-epicephems into 1-oxacephems

7-Epi-1-oxacephem was obtained by stereospecific, intramolecular etherification of alcohol prepared from 7-epicephems via aldehyde or formate. Synthesis of the 3-acetoxymethyl analogwas unsuccessful. Biologically active 1-oxacephems were derived from by known processes.