One‐Pot Stereoselective Synthesis of 2‐Acylaziridines and 2‐Acylpyrrolidines from N‐(Propargylic)hydroxylamines

The stereoselective direct transformation of N‐(propargylic)hydroxylamines into cis‐2‐acylaziridines was achieved by the combined use of AgBF₄ and CuCl. Copper salts were found to promote the transformation of the intermediary 4‐isoxazolines into 2‐acylaziridines and both 3‐aryl‐ and 3‐alkyl‐substituted 2‐acylaziridines could be prepared by using this method. Furthermore, subsequent 1,3‐dipolar cycloaddition of azomethine ylides that were generated in situ from the intermediary 2‐acylaziridines with maleimides was achieved in a stereoselective one‐pot procedure to afford the corresponding 2‐acylpyrrolidines, which consisted of an octahydropyrrolo[3,4‐c]pyrrole skeleton.     

2-Chloroanthraquinone-catalyzed aerobic photo-oxidative synthesis of diacylamines from benzylamides

In this Letter, we report the aerobic photo-oxidative synthesis of diacylamines from benzylamides in the presence of molecular oxygen and catalytic amounts of 2-chloroanthraquinones under visible light irradiation from a fluorescent lamp.     

Reaction of a Dialumene‐Benzene Adduct with Diphenylacetylene: Formation of 3,4‐Dialuminacyclobutene and 5,6‐Dialuminabicyclo[2.1.1]hex‐2‐ene Derivatives

Reaction of a dialumene‐benzene adduct bearing bulky aryl substituents with diphenylacetylene was found to give a novel 5,6‐dialuminabicyclo[2.1.1]hex‐2‐ene derivative in addition to the 3,4‐dialuminacyclobutene derivative, the formal [2+2]cycloadduct of an intermediary dialumene with diphenylacetylene. The molecular structure of the newly obtained 5,6‐dialuminabicyclo[2.1.1]hex‐2‐ene has been elucidated by X‐ray crystallographic analysis.     

Mesoporous Silica Particles as Topologically Crosslinking Fillers for Poly(N‐isopropylacrylamide) Hydrogels

Here it is demonstrated that mesoporous silicas (MPSs) can be used as effective “topological crosslinkers” for poly(N‐isopropylacrylamide) (PNIPA) hydrogels to improve the mechanical property. Three‐dimensional bicontinuous mesporous silica is found to effectively reinforce the PNIPA hydrogels, as compared to nonporous silica and two‐dimensional hexagonally ordered mesoporous silica.     

Facile Synthesis of Dibenzopentalene Dianions and Their Application as New π‐Extended Ligands

Reduction of phenyl(silyl)ethynes with potassium followed by quenching with iodine gave dibenzopentalenes in moderate yields. The intermediates of the reactions, dipotassium dibenzopentalenides, were isolated. The first dibenzopentalene–transition‐metal complex was successfully synthesized. The ruthenium atoms are located above the six‐membered rings. However, X‐ray diffraction analysis and theoretical calculations revealed that the aromatic nature of the five‐membered rings was retained. The cyclic voltammetry of the Ru complex revealed two oxidation waves with relatively large separation.     

Ein zus?tzlicher Test zur modernen Theorie der Molekulargewichts-Fraktionierung auf Grund der L?slichkeits-Differenz

Ohne Zusammenfassung     

Asymmetric hydrogenation of N-sulfonylated-alpha-dehydroamino acids: toward the synthesis of an anthrax lethal factor inhibitor

A novel and highly enantioselective Ru-catalyzed hydrogenation of N-sulfonylated-alpha-dehydroamino acids has been discovered and demonstrated in the synthesis of an anthrax lethal factor inhibitor (LFI). Herein, this methodology is used to prepare N-sulfonylated amino acids in up to 98% ee. This unprecedented hydrogenation uses a chiral Ru catalyst rather than Rh as typical for acylated dehydroamino acids and esters, and this work reports the first asymmetric hydrogenation of a tetrasubstituted dehydroamino acid derivative using a Ru catalyst. [reaction: see text]     

Age-dependent plasticity in the superior temporal sulcus in deaf humans: a functional MRI study

Background  

Sign-language comprehension activates the auditory cortex in deaf subjects. It is not known whether this functional plasticity in the temporal cortex is age dependent. We conducted functional magnetic-resonance imaging in six deaf signers who lost their hearing before the age of 2 years, five deaf signers who were >5 years of age at the time of hearing loss and six signers with normal hearing. The task was sentence comprehension in Japanese sign language.     

Manipulation of Particles with Counter-Propagating Evanescent Waves

Two counter-propagating evanescent beams are used to align and manipulate polystyrene particles on a prism surface. Since the radiation pressure transferred laterally from the evanescent wave is negated on both sides, particles can be stably aligned. By projecting a circular and a linear beam spot onto the interface, both multiple and single arrays of particles are achieved. Arrays of particles trapped on the interface can be easily moved adjusting the intensity of incident beams on either side. We also simulate electromagnetic distribution of scattering light that is converted from the evanescent wave using the FDTD method. The results show that scattering light converts from an evanescent wave propagating through a particle array and has a distance longer than that propagating from a normal evanescent wave.     

One-step synthesis of hierarchical porous γ-alumina with high surface area

Hierarchical porous γ-alumina is successfully fabricated from a precursor solution consisting of surfactants, polystyrene (PS) spheres, inorganic salts and solvents. After calcinations, uniform macropores are closely packed. The macropore size coincides with the original PS sphere size. These macropores are connected by small windows. In addition, the macropore walls have mesoporous structures, as confirmed by SAXS measurement and TEM observation. After calcination at 900 °C, the amorphous alumina frameworks are converted to the crystallized γ-alumina phase. Even after crystallization, the existence of uniform mesopores and high surface are well retained, though the mesoporous ordering is lower.