Optimization of asymmetric hydrogenation of 3-phenyl-3-butenoic acid catalyzed by rhodium(I)-4,5-bis[(diphenylphosphino)methyl]-2,2-dimethyldioxolane (DIOP)

Enantioselective, homogeneous hydrogenation of 3-phenyl-3-butenoic acid (1) has extensively been examined in the presence of the rhodium(I)/4,5-bis[(diphenylphosphino)methyl]-2,2-dimethyldioxolane (DIOP) catalyst systems. Optimization of the reaction conditions was undertaken mainly by controlling effects of added tertiary amines as well as solvent polarities on the enantio-selectivity of the product. The best asymmetric yield (85.1% e.e.) was attained when the hydrogenation was carried out in the presence of triethylamine (5 mol%) in 75% aqueous methanol using a neutral rhodium-DIOP catalyst.     

Luminance and Chromaticity Conditions of a Bichromatic Cross Pattern for Chromatically-Uniform Transparency

We can perceive a surface through another surface. This perception is called transparency. It is known that transparency can be perceived even if the stimulus conditions are not consistent with physical conditions for a real transparent surface. In this study, we measured the ranges of luminance and chromaticity of the overlapping area of two crossed layers at which a surface was perceived as chromatically-uniform transparent. As the results, the luminance range of the overlapping area existed around or near the luminance of the inducing area. The upper and lower limits of the luminance range were higher for the dark background than for the light background. Moreover, the chromatic range existed around the additive colormixture line between two chromaticities of the inducing areas for both dark and light backgrounds. This indicates that the perceptual transparency mechanism would divide the color of an additive color mixture into the original colors that exist in the inducing areas. We noticed that the perceptual appearance of the stimulus changed greatly depending on the luminances of the overlapping area and the background. These differences in perceptual appearance would be a factor explaining individual difference and deciding the luminance conditions for transparency.     

Analysis of banding problem in multiple beam scanning system of laser printer

In the slant scanning method of multiple beams a misalignment of the slant angle causes a beam spacing error and pitch irregularities of scan lines called “banding”. This paper evaluates the pitch irregularities and tries to clarify the allowable beam spacing error. The following results are obtained: (1) The maximum spacing error of print lines is proportional to m/(dpi), where m is the number of multiple beams and dpi print dot density. (2) The noticeable limit of periodic variations of print density at low spatial frequency was presumed to be a visibility between 1 and 2% in experiments. (3) The allowable beam spacing error was calculated introducing the human eye spatial frequency response. (4) The banding simulation experiments by laser recording on the photographic paper on the XY stage showed good coincidence with the theoretical evaluations.     

Synthetic studies on psiguadial B: Construction of bicyclo[4.3.1]decane skeleton via double cyclization reaction of alkyne dicobalt complex

A new method for constructing the polycyclic skeleton of psiguadial B (1), a meroterpenoid isolated from an evergreen shrub of Myrtaceae, was developed. The terpenoid substructure of 1 was constructed on the basis of a cascade double cyclization reaction of an alkyne dicobalt complex, which afforded the bicyclo[4.3.1]decane derivative having a benzyl group with the correct configuration. The substituted aromatic ring was introduced to the bridgehead position of the intermediate, and bromination under radical conditions followed by intramolecular cyclization reaction resulted in formation of the benzopyran moiety in a stereoselective manner.     

Solvent effect of ionic liquids on the distribution constant of 2-thenoyltrifluoroacetone and its nickel(II) and copper(II) chelates and the evaluation of the solvent properties based on the regular solution theory

Distribution constants of 2-thenoyltrifluoroacetone (Htta) and its Ni(II)and Cu(II) chelates between 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (C_nmimTf₂N; n = 4, 6, and 8) as ionic liquid (IL) and an aqueous phase were determined. The enol fraction of Htta in ILs was spectrophotometrically measured to calculate the distribution constant of the enol form (K_D,HE) of Htta. The K_D,HE values in ILs were evaluated by comparing those in various molecular solvents such as alkanes, aromatic hydrocarbons, chlorohydrocarbons, ethers, ketones, and esters previously reported on the basis of the regular solution theory (RST). It was elucidated that the IL solutions of Htta (enol) can be taken as apparently regular solutions as expected in the organic solvents. On the other hand, the effect of ILs on the distribution constant of metal(II) chelates (K_D,M) was fairly complicated. The Cu(tta)₂-IL solutions behaved like the alkane and aromatic hydrocarbon solutions but the Ni(tta)₂-IL (C₄mimTf₂N) like ether and ketone solutions. In the Ni(II) case, some specific interactions between the Ni(II) chelate and IL was suggested. Finally, the solubility parameters of ILs were calculated using K_D,HE by RST and were in good agreement with the literature values obtained by the enthalpy of vaporization.     

Unexpectedly stable artificial duplex from flexible acyclic threoninol

A new foldamer, acyclic threoninol nucleic acid (aTNA), has been synthesized by tethering each of the genetic nucleobases A, G, C, and T to d-threoninol molecules, which were then incorporated as building blocks into a scaffold bearing phosphodiester linkages. We found that with its fully complementary strand in an antiparallel fashion, the aTNA oligomer forms an exceptionally stable duplex that is far more stable than corresponding DNA or RNA duplexes, even though single-stranded aTNA is rather flexible and thus does not take a preorganized structure.