1,2-silyl-migrative cyclization of vinylsilanes bearing a hydroxy group: stereoselective synthesis of multisubstituted tetrahydropyrans and tetrahydrofurans(1)

Acid-catalyzed intramolecular addition of a hydroxy group to alpha-alkylated vinylsilanes has been studied. Treatment of (Z)-5-alkyl-5-silyl-4-penten-1-ols 1 (R = alkyl) with 5 mol % TiCl(4) in CHCl(3) gave trans-2-alkyl-3-silyltetrahydropyrans 2 exclusively (trans/cis = >99/1 to 97/3). The cyclization efficiency and rate strongly depended on the geometry of the C-C double bond and the silyl group. The use of (E)-vinylsilanes resulted in lower yields with poor cis-selectivity. In the cyclization of (Z)-1 (R = Bu), the silyl group used, the reaction time, and the yield of 2 were as follows: SiMe(2)Ph, 9.5 h, 75%; SiMe(3), 7.5 h, 66%; SiMePh(2), 24 h, 58%; SiMe(2)-t-Bu, 0.75 h, 85%; SiMe(2)Bn, 1.5 h, 78%. This 1,2-silyl-migrative cyclization could be applied to stereoselective synthesis of trisubstituted tetrahydropyrans. The acid-catalyzed reaction of 1-, 2-, or 3-substituted (Z)-5-silyl-4-nonen-1-ols 8 gave r-2,t-3,c-6-, r-2,t-3,t-5-, or r-2,t-3,c-4-trisubstituted tetrahydropyrans with high diastereoselectivity, respectively. (Z)-4-Alkyl-4-silyl-3-buten-1-ols 5 as well as 1 underwent the 1,2-silyl-migrative cyclization to give 2-alkyl-3-silyltetrahydrofurans 6 with high trans-selectivity. This silicon-directed cyclization was also available for the stereoselective synthesis of tri- and tetrasubstituted tetrahydrofurans.     

Electrochemically driven clathration/declathration of ferrocene and its derivatives by a nanometer-sized coordination cage

The electrochemical, NMR, and crystallographic studies clearly indicate that the clathration and declathration of ferrocene and its derivatives in a self-assmbled Pd(II)-linked nanometer-sized cage can be controlled by the oxidation state of the guest. Namely, the guests are clathrated when they are reduced but declathrated when they are oxidized. The process is rapid on the NMR time scale but slow on the CV time scale.     

Direct observation of the multistep helix formation of poly-L-glutamic acids

The helix formation dynamics of poly-L-glutamic acids (PGAs) were observed by the microsecond-resolved Fourier transform infrared (FTIR) and circular dichroism (CD) spectroscopies. The helix formation of 34-residue PGA from random coil at pH (or pD for FTIR) 8.0 was initiated by a pH jump to 4.9 using the rapid solution mixer whose mixing dead time is 50 micros. The amide I' line in the time-resolved FTIR spectra exhibited the fast (<100 micros) increase of the total helical content. The time-resolved CD spectra of the same process also showed the fast (<150 micros) formation of short helical segments (5 +/- 1 residues), which was followed by the slower (<1 ms) elongation of the short helices to longer helices (>10 residues). Similar dynamics were observed for the same pH jump of approximately 190-residue PGA, although there were additional steps that made the helix formation of approximately 190-residue PGA more complex. The observed multistep helix formation is likely caused by the strong hydrogen-bonding interactions between the protonated side chains of PGAs.     

Dissipative structures formed in the course of drying the colloidal crystals of silica spheres on a cover glass

Macroscopic and microscopic dissipative structural patterns formed in the course of drying the deionized aqueous colloidal crystal suspensions of silica spheres (diameter: 103 nm) on a cover glass have been observed. Spoke-like and ring-like patterns are formed in the macroscopic scale; the former is the crack in the sphere film and the latter is the hill accumulated with spheres formed around the outside edge. The neighbored inter-spoke angle, thickness of the film, and other morphological parameters have been discussed as a function of sphere concentration, concentration of sodium chloride, and the inclined angle of the cover glass. Fractal patterns of the mud cracks are observed in the microscopic scale. Capillary forces between spheres at the air-liquid surface and the relative rates between the water flow at the drying front and the convection flow of spheres are important for the pattern formation. Electronic Publication     

Flow amperometric detection of indigo for enzyme-linked immunosorbent assays with use of screen-printed electrodes

A simple and automated methodology for a sensitive electrochemical detection of enzyme immunoassays that employ alkaline phosphatase (AP) as label has been developed. A flow injection system with programmable pump, valve and cell functions, amperometric detection of indigo and screen-printed electrodes (SPEs) are responsible for the advantages of this methodology. Amperometric detection at a low potential of indigo, the product of the enzymatic hydrolysis of the substrate 3-indoxyl phosphate (IP), is combined with a flow injection system. This incorporates in the flow cell a disposable screen-printed board provided with a graphite working electrode. No electrode pretreatment is necessary to obtain reproducible signals. The system was applied to the determination by an enzyme-linked immunosorbent assays (ELISA) of pneumolysin (PLY), a toxin related to respiratory infections. Linear calibration curves for low and high concentration ranges were obtained. These were also performed in a proteic matrix and linearity was also obtained.     

Synthesis of polymers in aqueous solutions: Synthesis of polysulfide by reaction of bis(4‐mercaptophenyl) sulfide with bis(4‐chloro‐3‐nitrophenyl) sulfone using various bases in aqueous solutions

The polycondensation of bis(4‐mercaptophenyl) sulfide (BMPS) with bis(4‐chloro‐3‐nitrophenyl) sulfone (BCNPS) was examined using various organic or inorganic bases in mixed solvents of N‐methyl‐2‐pyrrolidone (NMP) with water or in plain water. The reaction of BMPS with BCNPS proceeded smoothly to give the corresponding polysulfide in mixed solvents of NMP with water at 60 °C using 1,8‐diazabicyclo[5.4.0]undecene‐7 as a base, although the rate of the reaction decreased gradually as the water in the solvent increased. Polysulfide can also be obtained by reaction in plain water using appropriate organic bases such as tripropylamine (TPA) or quinoline. The polysulfide with a number‐average molecular weight of 45,100 was synthesized in 62% yield when the reaction of BMPS with BCNPS was performed using TPA as a base at 60 °C for 48 h in plain water. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3399–3404, 2000     

Synthesis and cation-binding properties of poly-and bis(thiacrown ether)s

Poly- and bis(thiacrown ether) derivatives in which some oxygen atoms of benzocrown ether moiety are replaced by sulfur atoms have been synthesized. Their cation-binding abilities were investigated by using the solvent extraction method. The poly- and bis(benzothiacrown ether)s showed great affinity for silver ion, being more excellent in the affinity than the corresponding monocyclic analogs. They, however, possess very poor cation-binding ability for alkali and alkaline-earth metal ions. The poly- and bis(thiacrown ether)s also bind mercuric ions effectively, whereas the corresponding monomeric analogs do not at all.     

Alkane Oxidation with Molecular Oxygen Using a New Efficient Catalytic System: N-Hydroxyphthalimide (NHPI) Combined with Co(acac)(n)() (n = 2 or 3)

A novel class of catalysts for alkane oxidation with molecular oxygen was examined. N-Hydroxyphthalimide (NHPI) combined with Co(acac)(n)() (n = 2 or 3) was found to be an efficient catalytic system for the aerobic oxidation of cycloalkanes and alkylbenzenes under mild conditions. Cycloalkanes were successfully oxidized with molecular oxygen in the presence of a catalytic amount of NHPI and Co(acac)(2) in acetic acid at 100 degrees C to give the corresponding cycloalkanones and dicarboxylic acids. Alkylbenzenes were also oxidized with dioxygen using this catalytic system. For example, toluene was converted into benzoic acid in excellent yield under these conditions. Ethyl- and butylbenzenes were selectively oxidized at their alpha-positions to form the corresponding ketones, acetophenone, and 1-phenyl-1-butanone, respectively, in good yields. A key intermediate in this oxidation is believed to be the phthalimide N-oxyl radical generated from NHPI and molecular oxygen using a Co(II) species. The isotope effect (k(H)/k(D)) in the oxidation of ethylbenzene and ethylbenzene-d(10) with dioxygen using NHPI/Co(acac)(2) was 3.8.     

Evidence and mechanisms of filling polymerization by plasma-induced graft polymerization

Using a plasma-induced graft polymerization technique, which is well known as a surface modification method, the grafted polymer was formed in pores of the porous material. This study examined the filling mechanism. Five thin porous films were sandwiched together, and employed as the substrate. The substrate was treated by plasma, and the change in surface tension and radical formation was measured for each sheet after the sheet was separated. The only surface on which surface-tension change was detected, was that of the sheet directly exposed to the plasma. Although plasma treatment made polymer radicals primarily on the outer surface of the sheet, the treatment also formed a few radicals inside the sheets. The radicals inside the sheets reacted with methylacrylate and grafted polymer formed in the pores. The location of grafted polymer depended on the balance between monomer diffusivity and reactivity. The grafting rate depended on which monomer solvent was used for the polymerization. Thus, the grafted membrane morphology could be controlled by varying the grating solvent composition. © 1996 John Wiley & Sons, Inc.