Counterion Effect in Cobaltate-Catalyzed Alkene Hydrogenation

We show that countercations exert a remarkable influence on the ability of anionic cobaltate salts to catalyze challenging alkene hydrogenations. An evaluation of the catalytic properties of [Cat][Co(η⁴-cod)₂] (Cat=K ( 1 ), Na ( 2 ), Li ( 3 ), (^Depnacnac)Mg ( 4 ), and N(ⁿBu)₄ ( 5 ); cod=1,5-cyclooctadiene, ^Depnacnac={2,6-Et₂C₆H₃NC(CH₃)}₂CH)]) demonstrated that the lithium salt 3 and magnesium salt 4 drastically outperform the other catalysts. Complex 4 was the most active catalyst, which readily promotes the hydrogenation of highly congested alkenes under mild conditions. A plausible catalytic mechanism is proposed based on density functional theory (DFT) investigations. Furthermore, combined molecular dynamics (MD) simulation and DFT studies were used to examine the turnover-limiting migratory insertion step. The results of these studies suggest an active co-catalytic role of the counterion in the hydrogenation reaction through the coordination to cobalt hydride intermediates.     

Chirality due to deuterium substitution: synthesis and circular dichroism of (+)(R) p -2,7-dideuterio-1,6-methano[10]annulene

Summary The title compound was prepared from (–)(S) _p -2,7-dibromo-1,6-methano[10]annulene by treatment withn-Bu-Li and subsequent quenching with D₂O. The optical rotations at four wavelengths and the circular dichroism spectrum are reported.

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Chiralität durch Deuterium-Substitution: Synthese und Circulardichroismus von (+)(R) _p -2,7-Dideuterio-1,6-methano[10]annulen (Kurze Mitt.)

Zusammenfassung Die Titelverbindung wurde aus (–)(S) _p -2,7-Dibrom-1,6-methano[10]annulen durch Umsetzung mitn-Bu-Li und nachfolgende Reaktion mit D₂O dargestellt. Optische Rotationen bei vier Wellenlängen und das Circulardichroismus-Spektrum wurden bestimmt.

     

Cylindrical polymer brushes

In recent years, research on cylindrical polymer brushes (or molecular bottlebrushes) has received significant attention. In this article, we discuss various strategies for their synthesis and the unique properties arising from their regular multibranched structure. Some recent advances in the application of cylindrical polymer brushes are highlighted. Amphiphilic core– shell cylindrical polymer brushes, for example, have been successfully used as single molecular templates for inorganic nanoparticle formation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3461–3481, 2005     

Crystal structure of a squalene cyclase in complex with the potential anticholesteremic drug Ro48-8071

Squalene-hopene cyclase (SHC) catalyzes the conversion of squalene into pentacyclic compounds. It is the prokaryotic counterpart of the eukaryotic oxidosqualene cyclase (OSC) that catalyzes the steroid scaffold formation. Because of clear sequence homology, SHC can serve as a model for OSC, which is an attractive target for anticholesteremic drugs. We have established the crystal structure of SHC complexed with Ro48-8071, a potent inhibitor of OSC and therefore of cholesterol biosynthesis. Ro48-8071 is bound in the active-center cavity of SHC and extends into the channel that connects the cavity with the membrane. The binding site of Ro48-8071 is largely identical with the expected site of squalene; it differs from a previous model based on photoaffinity labeling. The knowledge of the inhibitor binding mode in SHC is likely to help develop more potent inhibitors for OSC.     

Sustainable photochemistry: solvent-free singlet oxygen-photooxygenation of organic substrates embedded in porphyrin-loaded polystyrene beads

A solvent-free photooxygenation process that uses organic substrates embedded in porphyrin-loaded polystyrene beads as solid support is described and applied for ene- and [4 + 2]-cycloaddition reactions involving singlet oxygen (1 delta g).     

Asymptotisches Verhalten der Maxima der Lösungen gewisser Differentialgleichungen

Eine oszillatorische Lösung u der Gleichung u" + qu = 0u' + qu = 0 hat die Wintner-Eigenschaft, wenn die relativen Maxima von q^1/4 |u|q^{1/4} |u| für t ? ￥t \to \infty gegen einen positiven endlichen Grenzwert streben. In Verallgemeinerung eines Satzes von Hartman werden neue Methoden zum Nachweis der Wintner-Eigenschaft beschrieben. Andererseits werden Funktionen q konstruiert, die belegen, daß i.a. das Verhalten von q^1/4 uq^{1/4} u fast beliebig ist. Durch Methoden aus dem Bereich der universellen Funktionen wird die Residualität solcher Funktionen q bewiesen.     

Der Zerfall des 2,4-sec100Nb

The nuclide¹⁰⁰Nb was produced by irradiation of enriched¹⁰⁰Mo targets with 14 MeV-neutrons, and its decay properties were investigated employing scintillation and semiconductor spectrometers and coincidence techniques. A half-life of 2.4±0.3 sec and aQ _β-value of 5.8±0.2 MeV were found. From 27 gamma-rays, 20 transitions, representing 95% of the observed gamma-ray intensity, could be placed in a decay scheme comprising 10 excited states of¹⁰⁰Mo.