Catalytic Enantioselective Addition of Nitro Compounds to Imines-A Simple Approach for the Synthesis of Optically Active beta-Nitro-alpha-Amino Esters

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Universality of the Local Spacing Distribution¶in Certain Ensembles of Hermitian Wigner Matrices

Consider an N×N hermitian random matrix with independent entries, not necessarily Gaussian, a so-called Wigner matrix. It has been conjectured that the local spacing distribution, i.e. the distribution of the distance between nearest neighbour eigenvalues in some part of the spectrum is, in the limit as N→∞, the same as that of hermitian random matrices from GUE. We prove this conjecture for a certain subclass of hermitian Wigner matrices. Received: 21 June 2000 / Accepted: 26 July 2000     

Electrical instability in a semiconductor gas discharge system

Electrical instability in a SI GaAs plates of the semiconductor gas discharge gap system (SGDGS) is studied experimentally in a wide range of the gas pressures, interelectrode distances and different diameters of the cathode areas. While being driven with a stationary voltage, it generates current and discharge light emission (DLE) instabilities with different amplitudes of the oscillation. It is shown that under the experimental conditions the interelectrode distance played only a passive role and was not responsible for the appearance of the DLE instability. At the same time for different diameters D of the GaAs plate areas the expanded range of current and DLE oscillations are observed. SGDGS with an N‐shaped CVC was analyzed using both the current and DLE data showing the electrical instability in the GaAs cathode. It was found that application of high feeding voltage to this cathode give rise to non‐uniform spatial distribution of the DLE, which disturbed the operation of the system. The experiment presents also a new metod to study and visualization of the electrical instabilities in high‐resistivity GaAs plates of large diameter. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ring enlargement reactions of tetramic acid derivatives

The 4‐hydroxypyridones 7 and 3‐hydroxypyridones 8/9 (azagrevellins) were prepared by reaction of the pyrrolidinetrione 4 and diazoalkanes. The ring enlargement proceeded by anionotropic [1,2]‐rearrangement introducing carbon between C‐3 and C‐4 or, to a lesser extent, between C‐2 and C‐3 due to the different migration aptitudes of the two acyl groups involved. In a cognate manner ring expansion between C‐2 and C‐3 occured by the interaction of diazomethane and the pyrrolidinetrione hydrazone 15 , to give the spiroe‐poxide 16 as the final product. From the reaction of trione 4 and diazomethane, however, the diepoxide 14 was obtained. In this case ring homologation must have taken place by insertion of carbon between C‐4 and C‐5. In a two step ring expansion the pyridones 21 and 22 were obtained from the maleineimides 17.     

Radical cyclisations of methylenecyclopropyl azetidinones—synthesis of novel tricyclic β-lactams

Addition of lithium bis(methylenecyclopropyl)cuprates to acetoxy azetidinones gives methylenecyclopropyl azetidinones, which can be converted to various radical cyclisation precursors. Attempted 4-exo cyclisation of 3 led only to reduced product, while cyclisation of 5, using CuCl/bipy, gave a carbacephem, via a 5-exo cyclisation, but in low yield. Cyclisation of 6 and 7, however, gave novel tricyclic β-lactams, as the result of 7-endo cyclisation, in good yield, and a cyclisation of bromide 23 led to the tricyclic β-lactam 24, via a radical cascade sequence.     

Single-component,low molecular weight organic supergelators based on chiral barbiturate scaffolds

ABSTRACT

We report here the first chiral barbiturate to act as a single-component LMOG capable of gelating a variety of chlorinated and aromatic solvents. Solution-based DOSY NMR experiments, solid-state VP-SEM, and X-ray crystallography techniques were used to characterize chloroform-based gels at a variety of size domains. This scaffold provides a simple system to study the dynamics of gelation and self-assembly.     

Dinuclear Molybdenum(II) Complexes with Thioether Functionalized Silylamide Ligands

Treatment of molybdenum(II) acetate with thioether functionalized silylamides R₂Si(NLi-C₆H₄–2-SR')₂ leads to the formation of dinuclear Mo^II complexes [Mo₂{R₂Si(NC₆H₄-2-SR')₂}₂]. According to X-ray crystal structure analyses the complexes [Mo₂{Me₂Si(NC₆H₄-2-SMe)₂}₂] and [Mo₂{Ph₂Si(NC₆H₄-2-SPh)₂}₂] comprise a Mo₂-unit which is coordinated by two μ-κ-N,N' silylamide ligands. The coordination sphere around the molybdenum atoms consists of two amide nitrogen atoms and two thioether sulfur atoms in a distorted square-planar arrangement. The Mo-Mo distances are 211.0(1) and 211.7(1) pm, resp. In the complex [Mo₂{Ph₂Si(NC₆H₄-2-SMe)₂}₂] the silyl amide units act as tetradentate κ-N,N',S,S'chelating ligands and the Mo-Mo distance is 218.6(1) pm.     

Plutonium and uranium accommodation in pyrochlore oxides

Fluorite-related ceramics have attracted considerable attention as potential host materials for the immobilisation of radionuclides. Here we have used computer simulation to investigate the relative solution energies and mechanisms for Pu³⁺, Pu⁴⁺ and U⁴⁺ accommodation in an extensive range of A₂B₂O₇ pyrochlore compounds. Solution is considered from simple oxides and via co-solution mechanisms. Results are discussed in terms of their implications for actinide retention and materials fabrication.