New synthetic method for orsellic acid type macrolides by intramolecular alkylation of protected cyanohydrin. The synthesis of (±)-zearalenone.

Zearalenone was synthesized by a general cyclization method of orsellic acid type macrolides having ketone moiety using the intramolecular alkylation of the protected cyanohydrin. This alkylation tolerates the presence of ester group and requires short reaction time.     

Antioxidant activity and mechanism of the abietane-type diterpene ferruginol

The antioxidant activity of the abietane-type diterpene ferruginol was evaluated by comparison with that of carnosic acid, ( ± )-α-tocopherol and dibutylhydroxytoluene using 2,2-diphenyl-1-picrylhydrazyl, β-carotene bleaching and linoleic acid assays. Ferruginol had the lowest antioxidant activity of this group using the 2,2-diphenyl-1-picrylhydrazyl and β-carotene methods in polar solvent buffer. However, ferruginol exhibited stronger activity than carnosic acid and α-tocopherol for linoleic acid oxidation under non-solvent conditions. Five peaks corresponding to ferruginol derivatives were detected through GC-MS analysis of the reaction between ferruginol and methyl linoleate. The three reaction products were identified as dehydroferruginol, 7β-hydroxyferruginol and sugiol, and the other two peaks were assumed to be 7α-hydroxyferruginol and the quinone methide derivative of ferruginol. The time course of the reaction suggests that the quinone methide was produced early in the reaction and reacted further to produce dehydroferruginol, 7-hydroxyferruginol and sugiol. Thus, we inferred that quinone methide formation was a key step in the antioxidant reaction of ferruginol.     

Influences of Acidic Conditions on Formazan Assay: A Cautionary Note

Formazan assay has been used for several decades to evaluate metabolic activity of eukaryotic and prokaryotic cells. In particular, it has been often applied for quantitative assessment of viable cells under acidic circumstances caused by, e.g., ischemia and hypoxia. However, little attention has been paid to the influence of acidic pH on formazan assays. We found that acidic culture conditions significantly affect outcomes of the assays. Absorbance of tetrazolium–formazan decreased in a pH-dependent manner without affecting cell viability. This nonspecific effect was ascribed to influences of acidic pH on the production of formazan. Replacement of culture media to fresh medium at physiologic pH partially overcame this problem. The influence of acidic culture conditions should be carefully considered when formazan assays are used for the assessment of viable cells under various experimental situations.     

1,4-Addition of silicon dienoates to α,β-unsaturated aldehydes catalyzed by in situ-generated silicon Lewis acid

In situ-generated silyl methide species (R(3)Si-CTf(2)R') effectively catalyzed the reaction of β-substituted α,β-unsaturated aldehydes with silicon dienoates such as 3-bromo-2-TESO-furan to give the corresponding γ-adducts with excellent 1,4-selectivity and good anti selectivity.     

Preparation, structure, and properties of tetranuclear vanadium(III) and (IV) complexes bridged by diphenyl phosphate or phosphate

Three novel tetranuclear vanadium(III) or (IV) complexes bridged by diphenyl phosphate or phosphate were prepared and their structures characterized by X-ray crystallography. The novel complexes are [{V(III)(2)(μ-hpnbpda)}(2){μ-(C(6)H(5)O)(2)PO(2)}(2)(μ-O)(2)]·6CH(3)OH (1), [{V(III)(2)(μ-tphpn)(μ-η(3)-HPO(4))}(2)(μ-η(4)-PO(4))](ClO(4))(3)·4.5H(2)O (2), and [{(V(IV)O)(2)(μ-tphpn)}(2)(μ-η(4)-PO(4))](ClO(4))(3)·H(2)O (3), where hpnbpda and tphpn are alkoxo-bridging dinucleating ligands. H(3)hpnbpda represents 2-hydroxypropane-1,3-diamino-N,N'-bis(2-pyridylmethyl)-N,N'-diacetic acid, and Htphpn represents N,N,N',N'-tetrakis(2-pyridylmethyl)-2-hydroxy-1,3-propanediamine. A dinuclear vanadium(IV) complex without a phosphate bridge, [(VO)(2)(μ-tphpn)(H(2)O)(2)](ClO(4))(3)·2H(2)O (4), was also prepared and structurally characterized for comparison. The vanadium(III) center in 1 adopts a hexacoordinate structure while that in 2 adopts a heptacoordinate structure. In 1, the two dinuclear vanadium(III) units bridged by the alkoxo group of hpnbpda are further linked by two diphenylphosphato and two oxo groups, resulting in a dimer-of-dimers. In 2, the two vanadium(III) units bridged by tphpn are further bridged by three phosphate ions with two different coordination modes. Complex 2 is oxidized in aerobic solution to yield complex 3, in which two of the three phosphate groups in 2 are substituted by oxo groups.     

Stereoselective synthesis of amphiasterin B4: assignment of absolute configuration

The first asymmetric synthesis of (+)-amphiasterin B4 was completed from a known (S)-β-benzyloxy-γ-lactone. Comparison with the spectroscopic properties reported for authentic material has given a clear indication as to the absolute stereochemistry of the natural amphiasterin B4.     

Concise Synthesis of Potassium Acyltrifluoroborates from Aldehydes through Copper(I)‐Catalyzed Borylation/Oxidation

Potassium acyltrifluoroborates (KATs) were prepared through copper(I)‐catalyzed borylation of aldehydes and subsequent oxidation. This synthetic route is characterized by the wide range of aldehydes accessible, favorable step economy, mild reaction conditions, and tolerance of various functional groups, and it enables the facile generation of a range of KATs, for example, bearing halide, sulfide, acetal, or ester moieties. Moreover, this method was applied to the three‐step synthesis of various α‐amino acid analogues that bear a KAT moiety on the C‐terminus by using naturally occurring amino acids as the starting material.     

Projection of Si 1s photoexcited orbitals into resonant Auger electron spectra in KLL decays of Si(CH3)4 and SiF4

Spectator resonant KL(23)L(23) Auger electron spectra have been measured in the Si 1s photoexcitation region of Si(CH(3))(4) using monochromatized undulator radiation combined with a hemispherical electron spectrometer. The broad peak with high intensity in a total ion yield spectrum, coming mainly from excitation of a 1s electron into the 6t(2) vacant orbital, induces a spectator Auger decay in which the excited electron remains in its excited orbital. The component on the higher energy side of this peak through 1s excitation into a Rydberg orbital produces resonant Auger decays in which the excited Rydberg electron moves into a slightly higher Rydberg orbital, or is partly shaken up to a significantly higher Rydberg orbital. These findings of Si(CH(3))(4) indicate a clear contrast to those for SiF(4), in which the 1s excitation into a Rydberg orbital induces a shake-down phenomenon as well as a shake-up one. The results of these molecules exhibit a clear splitting effect among excited orbitals which are smeared out by overlapping due to lifetime widths and due to densely populated levels in the 1s electron excitation spectrum. This is consistent with the calculation on photoexcitation within the framework of density functional theory.     

NO reduction by C3H6 over apatite-type A10(PO4)6(OH)2 (A?=?Ca and Sr)-supported Pt catalysts

A₁₀(PO₄)₆(OH)₂ (A = Ca and Sr)-supported Pt catalysts were prepared and their catalytic activity in NO reduction were investigated. The Sr₁₀(PO₄)₆(OH)₂-supported catalyst had high catalytic activity in the C₃H₆?CNO?CO₂ reaction; the activity was higher than that of the ??-Al₂O₃-supported catalyst at 300 °C. The basicity of the apatite supports would affect the chemical state of Pt on catalyst, resulting in promotion of NO reduction.     

Kinetics of radiation-induced grafting reactions. I. Polyethylene–styrene systems

By means of bromine labeling and ESR, the grafting reactions of styrene onto preirradiated polyethylene have been investigated. Not all the radicals produced by irradiations participate in grafting reactions all together, but they are rendered active bit by bit by the swelling of crystalline parts of polyethylene. The growing rates for polystyryl graft chains at 20°C decrease from 4 monomer units/active site/sec to one-fourth the initial value after 100 min. On the contrary, the average lifetimes increase from <10³ sec to >2.6 × 10³ sec. The number-average molecular weight of graft chains also increases with reaction times and rises to 3.5 × 10⁵ after 90 min at 20°C.