Photoinduced diastereoselective addition of perfluoroalkyl iodides to acrylic acid derivatives for the synthesis of fluorinated amino acids

Photoinduced diastereoselective addition of perfluoroalkyl iodides in the presence of an aqueous solution of Na2S2O3 was an excellent method for iodoperfluoroalkylation of acrylic acid derivatives bearing a chiral auxiliary, with moderate to good stereoselectivities and with no detectable side products. The iodoperfluoroalkylation of N-acyloylcamphorsultam provided a convenient route for preparing chiral fluorine-containing amino acids.     

Oxidative decarboxylation of α-keto carboxylic acids by carbonyl oxides

Photosensitized oxygenation of α-keto carboxylic acids in the presence of diazo compounds afforded the corresponding carboxylic acids and carbon dioxide in high yields; oxidative decarboxylation by carbonyl oxides occurred.     

Ferric superoxide and ferric hydroxide are used in the catalytic mechanism of hydroxyethylphosphonate dioxygenase: a density functional theory investigation

Hydroxyethylphosphonate dioxygenase (HEPD) is a mononuclear nonheme iron enzyme that utilizes an O(2) molecule to cleave a C-C bond in 2-hydroxyethylphosphonate and produce hydroxymethylphosphonate (HMP) and formic acid. Density functional theory calculations were performed on an enzyme active-site model of HEPD to understand its catalytic mechanism. The reaction starts with H-abstraction from the C2 position of 2-HEP by a ferric superoxide-type (Fe(III)-OO(?-)) intermediate, in a similar manner to the H-abstraction in the reaction of the dinuclear iron enzyme myo-inositol oxygenase. The resultant Fe(II)-OOH intermediate may follow either a hydroperoxylation or hydroxylation pathway, the former process being energetically more favorable. In the hydroperoxylation pathway, a ferrous-alkylhydroperoxo intermediate is formed, and then its O-O bond is homolytically cleaved to yield a complex of ferric hydroxide with a gem-diol radical. Subsequent C-C bond cleavage within the gem-diol leads to formation of an R-CH(2)(?) species and one of the two products (i.e., formic acid). The R-CH(2)(?) then intramolecularly forms a C-O bond with the ferric hydroxide to provide the other product, HMP. The overall reaction pathway does not require the use of a high-valent ferryl intermediate but does require ferric superoxide and ferric hydroxide intermediates.     

High pressure synthesis and properties of ternary titanium (III) fluorides in the system KF-TiF3 containing regular pentagonal bipyramids [TiF7]

Titanium trifluoride TiF₃ has the distorted ReO₃ structure composed of corner sharing TiF₆ octahedra linked with Ti-F-Ti bridges. Potassium fluoride KF was inserted into the bridges using high-pressure and high-temperature conditions (5 GPa, 1000-1200 °C). When the molar ratio KF/TiF₃≥1, a few low dimensional compounds were obtained forming non-bridged F ions. At the composition KF/TiF₃=1/2, a new compound KTi₂F₇ was formed, which crystallizes with the space group Cmmm and the lattice parameters of a=6.371(3), b=10.448(6), c=3.958(2) Å, consisting of edge-sharing pentagonal bipyramids [TiF₇] forming ribbons running along the a axis. The ribbons are linked by corners to construct a three-dimensional framework without forming non-bridged F ions. The compound is antiferromagnetic with the Néel temperature T_N=75 K, and the optical band gap was 6.4 eV. A new fluoride K₂TiF₅ (KF/TiF₃=2) with the space group Pbcn and the lattice parameters of a=7.4626(2), b=12.9544(4) and c=20.6906(7) Å was also obtained by the high pressure and high temperature treatment (5 GPa at 1000 °C) of a molar mixture of 2 KF+TiF₃. The compound contains one-dimensional chains of corner-sharing TiF₆ octahedra.     

Potassium tert-butoxide-mediated regioselective silaboration of aromatic alkenes

The regio- and diastereoselective silaboration of aromatic alkenes with a silylboron compound proceeds in the presence of a catalytic amount of potassium tert-butoxide, providing a complementary method to the corresponding transition metal-catalyzed reactions.     

Copper(II)/phenanthroline-mediated CD-enhancement and chiral memory effect on a meta-ethynylpyridine oligomer

meta-Ethynylpyridine 18-mer associates with octyl β-D-glucopyranoside to show an induced circular dichroism (CD) band at around 337 nm in CH(2)Cl(2). The addition of copper(II) triflate and o-phenanthroline enhanced the CD band. Even when an equimolar amount of β-L-glucopyranoside was added to make the system racemic, the CD was memorized and remained for several weeks.     

Raman band shapes and the dynamics of liquid N2O4

The Raman spectra of the totally symmetric A _g modes, v ₁, v ₂ and v ₃, of the N₂O₄ molecule have been measured in the liquid state at 262, 279 and 297 K. The vibrational and the rotational correlation functions are calculated. The long-time exponential decay of the rotational correlation functions of all the A _g modes reflects an asymptotic diffusional behaviour of molecular reorientation. The rotational relaxation rate is found to increase with increasing temperature. A marked point of inflection from the short time inertial correlation to the long time exponential decay appears at about 0·35 ps for the v ₂ mode. This is an indication of orientational rebound arising from the librational motion in a temporary solvent cage. The isotropic bandwidth increases in the order v ₁ < v ₂ < v ₃, which is also the order of decreasing vibrational frequency. The temperature dependence of the peak frequency and of the bandwidth are also found to increase in the same order. These observations are analysed qualitatively in terms of two models of vibrational dephasing which take into account the effect of vibrational anharmonicity.     

Helix formation in synthetic polymers by hydrogen bonding with native saccharides in protic media

Water-soluble poly(m-ethynylpyridine)s were designed to realize saccharide recognition in protic media. UV/Vis, 1H NMR, and fluorescence measurements revealed that the polymer forms a helical higher order structure by solvophobic interactions between the ethynylpyridine units in the protic medium. The resulting pore in the helix behaves like a binding pocket in proteins, by taking advantage of inwardly directed hydrogen-bonding functional groups of the polymers. Molecular recognition of native saccharides by the polymers was investigated by circular dichroism (CD). The chirality of the saccharide was transferred to the helical sense of the polymers, accompanied by the appearance of induced CDs (ICDs) in the absorptive region of the polymers. In MeOH/water (10/1), mannose and allose showed intense ICDs, and the apparent association constant between the polymer and D-mannose was 14 M(-1).     

Comparison of the compact dry YM with the FDA BAM method for enumeration of yeasts and molds in fruit-based products. Performance-Tested Method 100401

Compact Dry YM is a ready-to-use test method for the enumeration of yeasts and molds in fruit-based products. The plates are presterilized and contain nonwoven incorporated nutrients supplemented with antibiotics and a chromogenic enzyme substrate, 5-bromo-4-chloro-3-indoxyl phosphate, p-toluidine salt (X-phos), to facilitate counting dyes, and a cold water-soluble gelling agent. The medium should be rehydrated with 1 mL of diluted sample inoculated onto the center of the self-diffusible medium, allowing the solution to diffuse immediately by capillary action. The plate can be incubated at 25 degrees C for 7 days. The Compact Dry YM medium plates were validated as an analysis tool determining colony forming units of yeasts and molds from a variety of fruit-based products using 5 different fruit products. The performance tests were conducted at 25 degrees C. In all studies performed, no apparent differences were observed between the Compact Dry YM method and the U.S. Food and Drug Administration's Bacteriological Analytical Manual (FDA BAM) method results (P > 0.05). For the accuracy claim (n = 75), a correlation factor of r2 = 0.99 could be assigned, as stated in the application for Performance-Tested Method.     

Effects of intermolecular vibrational coupling and liquid dynamics on the polarized Raman and two-dimensional infrared spectral profiles of liquid N,N-dimethylformamide analyzed with a time-domain computational method

A time-domain method for calculating polarized Raman and two-dimensional infrared (2D-IR) spectra that includes the effects of both the diagonal frequency modulations (of individual molecules in the system) and the off-diagonal (intermolecular) vibrational coupling is presented and applied to the case of the amide I band of liquid N,N-dimethylformamide. It is shown that the effect of the resonant off-diagonal vibrational coupling and the resulting delocalization of vibrational modes is clearly seen as the noncoincidence effect in the polarized Raman spectrum and some spectral features (especially as asymmetric intensity patterns) in the 2D-IR spectra. The type of 2D-IR spectra (concerning the polarization condition) most appropriate for observing this effect is discussed. On the basis of the agreement between the observed and calculated band profiles of the polarized Raman spectrum, the time dependence of the transient IR absorption anisotropy is also calculated. The method of evaluating the extent of delocalization of vibrational modes that is relevant to the features of these optical signals in the time and frequency domains is discussed. The nature of the molecular motions (concerning the liquid dynamics) that are effective on the diagonal frequency modulations is also examined.