C3-symmetric trisimidazoline-catalyzed enantioselective bromolactonization of internal alkenoic acids

A method for conducting enantioselective bromolactonization reactions of trisubstituted alkenoic acids, using the C(3)-symmetric trisimidazoline 1 and 1,3-dibromo-5,5-dimethyl hydantoin as a bromine source, has been developed. The process generates chiral δ-lactones that contain a quaternary carbon. The results of studies probing geometrically different olefins show that (Z)-olefins rather than (E)-olefins are favorable substrates for the process. The method is not only applicable to acyclic olefin reactants but can also be employed to transform cyclic trisubstituted olefins into chiral spirocyclic lactones. Finally, the synthetic utility of the newly developed process is demonstrated by its application to a concise synthesis of tanikolide, an antifungal marine natural product.     

Liver function assessment with three (13)C breath tests by two-point measurements

In this study, we performed three breath tests - l-[1-(13)C ]phenylalanine breath test (PBT), l-[1-(13)C ] methionine breath test, and [(13)C]methacetin breath test (MethaBT) - in patients with chronic liver disease to determine the optimal timing of expired air collection for diagnosing chronic liver disease and evaluating the grade of fibrosis. The subjects were 61 adults with normal livers, 98 chronic hepatitis patients, and 91 liver cirrhosis patients. We investigated the relationships of breath test results with routine biochemical tests and the Child-Pugh score, as well as the diagnostic capacities of the breath tests for liver dysfunction/cirrhosis and grade of liver fibrosis. For the diagnosis of liver cirrhosis and correlations with liver fibrosis, the accuracy of the PBT at 30 min (PBT30) was similar to that of the MethaBT at 15 min (Metha15). For liver function assessment by two-point measurement with (13)C breath tests, we recommend the PBT30 and the Metha15.     

Gravitational compression dynamics of charged colloidal crystals

We examine the compression of charged colloidal crystals under the influence of gravitational force by monitoring the spatiotemporal variations of Bragg diffraction from the crystal lattice. We use the dilute aqueous dispersions of colloidal silica particles (diameter=216 nm, charge number=733, a particle volume fraction φ=0.06) in the presence of 5-15 μM sodium chloride. The sedimentation profiles of the colloidal crystals along the crystal height are determined by in situ fiber optics reflection spectroscopy. The time evolutions of the sedimentation profiles are calculated by numerical simulations based on a phenomenological continuum model that explicitly incorporates the electrostatic interparticle interactions. The simulation results correctly describe the experiments at sufficiently high ionic strength.     

Cobalt carbonyl catalyzed reduction of aromatic nitriles with a hydrosilane leading to N,N-disilylamines

Cobalt carbonyl catalysed reaction of HSiMe₃ with aromatic nitriles having various functional groups provided a novel route to $\text{N,N}$-disilylamines.     

Developments of magnetic-resonance-related spin chemistry in Japan

A review on the developments of the magnetic-resonance-related spin chemistry in Japan is presented. We describe how studies in this area started in Japan and developed into the flourishing state of the present. Important contributions made by Japanese spin chemists in the last two decades in three areas, namely, work on chemically induced dynamic electron polarization, excited states and controlling of photochemical reactions, are presented. More emphases are placed on the new developments in recent years, particularly new concepts and new methodologies.     

Tight inclusion of an acid guest into the cavity of cyclodextrin bearing an amino moiety in dimethyl sulfoxide

Circular dichroism measurements show that β-cyclodextrin with an amino moiety has a strong binding ability for ferrocenecarboxylic acid in dimethyl sulfoxide via an acid-base interaction.     

Two color oscillations of TE-CO2 laser and applications to two photon process of optically pumped FIR laser

We have developed the resonance system which is able to operate a TE-CO₂ discharge tube in two color emission source. The two color source is excellent in pumping efficiency, spacial overlap and time synchronization of the two emission CO₂ lines.We indicate that the competitive operation of the two emissions is well explained by a simple model.When a TE-CO₂ laser operates at the total pressure of below half atmospheric pressure, we make clear in this work that the operation of a TE-CO₂ laser forms depression like hole burning, with regards to the J of the upper laser level by J-J collisional relaxation during the laser emission.As an example of the two-photon source, two-photon pumping of NH₃ and FIR emissions are given in this paper.     

Mild and efficient removal of hydroxyethyl unit from 2-hydroxyethyl ether derivatives leading to alcohols

[reaction: see text]. CAN is a good reagent for the transformation of 2-hydroxyethyl ether units to alcohols. Significantly, many functional groups can tolerate the reaction conditions, although they do not survive under many previously reported removal conditions. The reaction mechanism is clarified.     

Studies aimed at the total synthesis of azadirachtin. A modeled connection of C-8 and C-14 in azadirachtin

[reaction: see text] Studies on the connection between the right and left segments of azadirachtin are described. The Ireland-Claisen rearrangement of Li-enolate of the modeled ester with dichlorodimethylsilane in toluene afforded the desired limonoid framework stereoselectively in good yield.     

Novel branched ether formation via conjugate reduction of an unsaturated cyanohydrin derivative and its synthetic application to the EF-ring segment of ciguatoxin

A synthetic method for a branched ether system was developed. The method was based on Lewis-acid-promoted γ-position selective reduction of a γ-alkoxy β,γ-unsaturated α-silyloxy nitrile, prepared through a process including intermolecular hetero-Michael reaction of a 2-butynoate ester derivative with an alcohol. The method was efficiently applied to the synthesis of fused medium-ring ethers involving the EF-ring segment (2) of ciguatoxin (1).