Total synthesis of leustroducsin B

A convergent total synthesis of leustroducsin B (1), which is known to exhibit a variety of biological activities, was successfully carried out. Notable features of our synthesis include construction of the C8 stereocenter by lipase-mediated desymmetrization of meso-diol 4 (90.2% ee) and preparation of the C9-C11 anti-diol moiety by the addition of alkynylzinc reagent 20 to the aldehyde 19. Furthermore, a new diol protecting group, p-silyloxybenzylidene, was developed for the deprotection from densely functionalized substrates under weakly acidic conditions. The protecting group was easily removed in a two-step procedure ((HF)3.Et3N; AcOH-THF-H2O).     

New avenues in dinitrogen fixation research

The present article focuses on a recent finding concerning dinitrogen fixation by using titanium oxide/conducting polymer composite systems and its comparison with an earlier fixation method (Schrauzer process) that makes use of a powdered titanium oxide. Both processes work under the stimulus of light at room temperature and pressure, but dinitrogen is fixed to a solid ammonium salt crystal in the former and to a gaseous ammonia molecule in the latter process. Differences in the physicochemical concepts between the two processes are discussed.     

An elementary construction of tilting complexes

Let A be an artin algebra and e∈A an idempotent with add(eA_A)=add(D(_AAe)). Then a projective resolution of Ae_eAe gives rise to tilting complexes for A, where P(l)^• is of term length l+1. In particular, if A is self-injective, then is self-injective and has the same Nakayama permutation as A. In case A is a finite dimensional algebra over a field and eAe is a Nakayama algebra, a projective resolution of eAe over the enveloping algebra of eAe gives rise to two-sided tilting complexes {T(2l)^•}_l?1 for A, where T(2l)^• is of term length 2l+1. In particular, if eAe is of Loewy length two, then we get tilting complexes {T(l)^•}_l?1 for A, where T(l)^• is of term length l+1.     

Rapid large-scale magnetic-field dissipation in a collisionless current sheet via coupling between Kelvin-Helmholtz and lower-hybrid drift instabilities

Rapid large-scale magnetic-field dissipation is observed in a full kinetic simulation of cross-field current instabilities in a current sheet even when the thickness of the current sheet is at ion scale. The Kelvin-Helmholtz instability caused by the velocity shear between the current-carrying ions and the cold background ions excites the lower-hybrid drift instability at the edges of the undulated current sheet. We show that the nonlinear coupling between these two instabilities is responsible for the observed rapid dissipation. The simulation result presents a new route for magnetic-field dissipation in an ion-scale current sheet and demonstrates the general significance of nonlinear cross-scale coupling in collisionless plasmas.     

Practical optical frequency measurement system around 1.5 μm based on an acetylene-stabilized laser-locked optical frequency comb

We have developed a practical and precise frequency measurement system at 1.5 μm telecommunication band. An electro-optic-modulator based optical frequency comb is phase-locked to a dither-free acetylene-stabilized laser to realize an optical frequency comb with frequency uncertainty of 10 kHz (5 × 10⁻¹¹) and the linewidth of 15 kHz. The present frequency comb can be also used as an optical frequency reference grid defined by ITU-T (International Telecommunication Union, Telecommunication Standardization Sector). Using the present frequency measurement system, we have demonstrated the first optical frequency measurement of ¹²C¹⁶O overtone absorption lines around 1.56 μm with the uncertainty of lower than 900 kHz.     

Synthesis of [60]fullerene-containing [2]rotaxanes using axle molecules bearing donor moiety

[2]Rotaxanes, consisting of a fullerene derivative bearing an electron-donating 1,5-dialkoxynaphthalene moiety and a macrocycle containing electron-deficient naphthalenetetracarboxylic diimide moieties, were first successfully synthesized and characterized.     

A new method for the high performance liquid chromatographic determination of TA-870, a dopamine prodrug (catechol ester compound)

A new method for the high performance liquid chromatographic (HPLC) determination of N-(N-acetyl-L-methionyl)-O,O-bis(ethoxycarbonyl)dopamine (TA-870), a dopamine prodrug, in biological fluid has been developed. In order to measure with an electrochemical detector (ECD), TA-870 was passed first through an immobilized carboxylesterase column to be converted to the electrochemically active deethoxycarbonylated TA-870 (DEC-TA-870). The properties of this carboxylesterase immobilized on Sepharose 4B were examined by this flow injection system. Hydrolysis of TA-870 with this immobilized carboxylesterase was a maximum at pH 7-8 and 50 degrees C, and the activity decreased in the presence of organic solvent such as acetonitrile. For the determination of TA-870 in biological fluids, an HPLC-immobilized enzyme-ECD system using a column-switching technique was developed. The blood was deproteinized with ethanol, and TA-870 in the ethanol extracts was adsorbed in Bond Elut C18. The dichloromethane eluate from Bond Elut C18 was injected into the HPLC system. The HPLC apparatus was composed of three pumps, two separation columns (LiChrosorb Si 60 and mu Bondasphere), a trap column (Bond Elut), an enzyme column, ECD and the column-switching system. The calibration curve for TA-870 in blood was linear in the range from 2 to 200 ng/mL. This new assay method might be useful also for the determination of other catechol ester compounds.     

Enantioselective preparation of C-ring fragment of cotylenin A via catalytic asymmetric intramolecular cyclopropanation of α-diazo β-keto ester

A synthetic pathway to the C-ring fragment of cotylenin A which emerged from our retrosynthetic analysis of cotylenin A is described. The catalytic asymmetric intramolecular cyclopropanation (CAIMCP) of the α-diazo-β-keto ester bearing 2,4,6-trimethylphenyl group as the ester part has been found to afford the crystalline product with high ee, which allowed to establish the approach to the C-ring fragment which required ten-pot operations. The developed approach would be beneficial to a large scale synthesis of the C-ring fragment for the total synthesis of cotylenin A.