Copper‐Catalyzed Electrophilic Amination of Heteroarenes and Arenes by CH Zincation

Direct amination of heteroarenes and arenes has been achieved in a one‐pot C? H zincation/copper‐catalyzed electrophilic amination procedure. This amination method provides an efficient and rapid approach to access a diverse range of heteroaromatic and aromatic amines including those previously inaccessible using C? H amination methods. The mild reaction conditions and good functional‐group compatibility demonstrate its great potential for the synthesis of important and complex amines.     

Nucleophilic Reactivity of a Copper(II)–Superoxide Complex

Metal‐bound superoxide intermediates are often implicated as electrophilic oxidants in dioxygen‐activating metalloenzymes. In the nonheme iron α‐ketoglutarate dependent oxygenases and pterin‐dependent hydroxylases, however, Fe^III–superoxide intermediates are postulated to react by nucleophilic attack on electrophilic carbon atoms. By reacting a Cu^II–superoxide complex ( 1 ) with acyl chloride substrates, we have found that a metal–superoxide complex can be a very reactive nucleophile. Furthermore, 1 was found to be an efficient nucleophilic deformylating reagent, capable of Baeyer–Villiger oxidation of a number of aldehyde substrates. The observed nucleophilic chemistry represents a new domain for metal–superoxide reactivity. Our observations provide support for the postulated role of metal–superoxide intermediates in nonheme iron α‐ketoglutarate dependent and pterin‐dependent enzymes.     

‘Click’ silica immobilisation of metallo-porphyrin complexes and their application in epoxidation catalysis

We present the synthesis, via Adler condensation reactions, of mono- and tetrakis-4-(ethynyl-phenyl)porphyrin ligands and the zinc and manganese complexes thereof. The formed complexes were immobilised on silica by reacting the ethynyl groups with azide-functionalised silica in a copper(I) catalysed Huisgens 1,3-dipolar cycloaddition reaction. The synthesised metallo-porphyrin containing materials were thoroughly characterised using various solid-state techniques (NMR, IR, UV-Vis, elemental content analysis). The manganese containing materials were applied as catalysts in the epoxidation of various alkenes (cyclooctene, cyclohexene, styrene) with various oxidants (iodosylbenzene, tert-butylperoxide). The heterogenised homogeneous catalysts show diminished activity and yields compared to the analogous homogeneous catalysts (71% yield cf. 92% for cyclooctene epoxidation, TOF 82 h⁻¹ cf. 230 h⁻¹). Upon recycling, the heterogenised catalysts become gradually less active over five cycles until they are catalytically inactive. The deactivation process is discussed, with spectroscopy suggesting that the catalysts themselves are intact and thus stable to the reaction conditions and recycling, however there is likely some decomplexation, and also both chemical and mechanical decomposition of the silica support resulting in inaccessibility to the catalytic site.     

Doping dependence of the pressure response of Tc in the SmO(1-x)F(x)FeAs superconductors

The superconducting transition temperature of the high-Tc SmO1-xFxFeAs superconductors increases monotonically as the F-doping level x increases to 0.20. High-pressure magnetization experiments reveal a strong sensitivity of Tc to interatomic distances in the underdoped regime (x 相似文献   

Crystal structure of the new FeSe(1-x) superconductor

The newly discovered superconductor FeSe(1-x) (x approximately 0.08, T(c)(onset) approximately 13.5 K at ambient pressure rising to 27 K at 1.48 GPa) exhibits a structural phase transition from tetragonal to orthorhombic below 70 K at ambient pressure-the crystal structure in the superconducting state shows remarkable similarities to that of the REFeAsO(1-x)F(x) (RE = rare earth) superconductors.     

An Optical Particle Counting System for Testing Industrial Pulse-Cleaned Cartridge Dust Collectors

An optical particle counting system has been developed for testing industrial pulse-cleaned cartridge dust collectors. The system is applied to measure fractional penetration of a full scale dust collector and to study its short term and long term dynamic behavior. Results show collector efficiencies for dust loadings of 23 g/m³ exceeding 99.999% over the particle size range from 0.5 μm to 10 μm, with a minimum fractional penetration occurring at approximately 2 μm.     

Renormalization-scale independence of the physical cosmological constant

Treating the metric as a classical background field, we show that the cosmological constant does not run with the renormalization scale—contrary to some claims in the literature.     

Reactions of terminal polyynes with benzyl azide

Terminal di-, tri-, tetra-, and pentaynes substituted with a variety of functional groups react with benzyl azide in the presence of CuSO(4)·5H(2)O and ascorbic acid to give derivatives of 4-ethynyl-, 4-butadiynyl-, 4-hexatriynyl-, and 4-octatetraynyl-1,2,3-triazoles in moderate to good yields. These reactions appear to proceed regioselectively, and functionalization occurs exclusively at the terminal alkyne moiety. As well, no evidence of multiple azide additions to the polyyne framework is observed. X-ray crystallographic analysis of nine derivatives is used to document the regioselectivity of the reaction as well as outline structural characteristics of the 1,2,3-triazole products.     

Gl2 of rings with many units

This paper describes the generiators and normal subgroups of GL₂(R) where R is a commutative ring with “many units”.