Thionation of ω‐Acylamino Ketones with Lawesson's Reagent: Convenient Synthesis of 1,3‐Thiazoles and 4H‐1,3‐Thiazines

The reaction of ω‐acylamino ketones with Lawesson's reagent (=2,4‐bis(4‐methoxyphenyl)‐1,3,2,4‐dithiadiphosphetane 2,4‐disulfide; LR ) is described. Treatment of 2‐acylamino ketones 1 (n=0) with LR gave 1,3‐thiazole derivatives 3 in good yields (Scheme 1 and Table 1). The 4H‐1,3‐thiazines 4 were obtained as main products by treatment of 3‐acylamino ketones 2 (n=1) with an equimolar amount of LR , while mainly the corresponding 3‐(thioacyl)amino ketones 5 were isolated when 0.5 equiv. of LR was used. The 3‐acylamino esters 7 also reacted with LR to give the corresponding 3‐(thioacyl)amino esters 8 (Scheme 3 and Table 2).     

Dynamic observations of the formation of thin Cu layers on clean and hydrogen-terminated Si(1 1 1) surfaces

The growth of Cu on the clean and hydrogen-terminated Si(1 1 1) surfaces is studied in situ by low-energy electron microscopy (LEEM). The dependence of the growth of the “5×5” layer on the clean Si(1 1 1) 7×7 surface upon the deposition temperature is investigated by combining LEEM with LEED. After completion of the “5×5” layer not only the regular-shaped three-dimensional islands reported before are observed but also irregular shaped more two-dimensional islands. On the hydrogen-terminated Si(1 1 1) surface the formation of the “5×5” structure is suppressed and nano-scale islands form preferentially at the step edges and domain boundaries. This is attributed to the enhancement of the surface migration of Cu atoms by the elimination of the surface dangling bonds.     

Anomalous conformational change in 1-butyl-3-methylimidazolium tetrafluoroborate-D2O mixtures

We have investigated the effect of deuterated water on the conformational equilibrium between the gauche and trans conformers of the [bmim] cation in mixtures of water and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)]), an ionic liquid, at room temperature. A comparison of the results obtained from solutions made with H(2)O and with D(2)O highlights an anomalous conformational change in the D(2)O solution showing an extended N-shaped behavior. The gauche conformer of the [bmim] cation in D(2)O increased up to x = ~50 (D(2)O mol %); however, it decreased up to higher water concentrations of x = ~85 before again increasing drastically toward x = ~100. We provide spectroscopic evidence that the anomalous conformational dynamics of the [bmim] cation in D(2)O is directly related to the H/D exchange reaction of the C-H group at position 2 of the imidazolium ring.     

Copper-catalyzed oxidative direct cyclization of N-methylanilines with electron-deficient alkenes using molecular oxygen

The oxidative direct cyclizaion of N-methylanilines with electron-deficient alkenes involving maleimides and benzylidene malononitriles through sp(3) and sp(2) C-H bond cleavage proceeds effectively under a CuCl(2)/O(2) catalysis to provide the corresponding tetrahydroquinolines in good yields.     

A characterization of totally <Emphasis Type="Italic">η</Emphasis>-umbilical real hypersurfaces and ruled real hypersurfaces of a complex space form

We give a characterization of totally η-umbilical real hypersurfaces and ruled real hypersurfaces of a complex space form in terms of totally umbilical condition for the holomorphic distribution on real hypersurfaces. We prove that if the shape operator A of a real hypersurface M of a complex space form M ⁿ (c), c ≠ 0, n ⩾ 3, satisfies g(AX, Y) = ag(X, Y) for any X, Y ∈ T ₀(x), a being a function, where T ₀ is the holomorphic distribution on M, then M is a totally η-umbilical real hypersurface or locally congruent to a ruled real hypersurface. This condition for the shape operator is a generalization of the notion of η-umbilical real hypersurfaces.     

Evaluation of homology modeling of the severe acute respiratory syndrome (SARS) coronavirus main protease for structure based drug design

To accelerate the development of drugs against severe acute respiratory syndrome (SARS), we constructed a homology model of the SARS coronavirus main protease using our modeling software, FAMS Ligand&Complex, and released it before the X-ray structure was solved. The X-ray structure showed our model as accurately predicted and useful for structure based drug design.     

Quantitative Auger electron spectroscopy analysis with co-evaporated AuCu films

A method for the quantitative Auger electron spectroscopy (AES) analysis by using a co-evaporation technique is extended to the AuCu system following the previous work. The calibration curves for lower Auger energy have peaks at 60 eV for Cu and at 69 eV for Au, and for higher Auger energy peaks at 239 eV for Au and at 920 eV for Cu. It is found that a simple linear relation does not exist in the results for AES measurements and the bulk analysis by atomic absorption spectroscopy (AAS) because of the back-scattering effect and the overlap of the spectra at lower energies in the Au-Cu system. It is also found that the adsorption of oxygen caused by electron beam bombardment has a significant influence on the AES results. The calibration curves obtained after a correction for oxygen adsorption are successfully applied to the determination of the composition at the surface of a sputtered AuCu alloy.