Immobilized cobalt/rhodium heterobimetallic nanoparticle-catalyzed silylcarbocylization and carbonylative silylcarbocyclization of 1,6-enynes

Reaction of 1,6-enynes with a hydrosilane in the presence of immobilized cobalt/rhodium bimetallic nanoparticles gives 2-methyl-1-silylmethylidene-2-cyclopentanes in the absence of carbon monoxide and 2-formylmethyl-1-silylmethylidene-2-cyclopentanes under 1 atm of carbon monoxide, respectively. [reaction: see text]     

Baylis-Hillman mechanism: a new interpretation in aprotic solvents

Using reaction rate data collected in aprotic solvents, we have determined that the Baylis-Hillman rate-determining step is second order in aldehyde and first order in DABCO and acrylate. On the basis of these data, we have proposed a new mechanism involving a hemiacetal intermediate. The proposed mechanism was then supported using two different kinetic isotope experiments.     

Ruthenium‐catalyzed synthesis of quinolines via reductive heteroannulation of nitroarenes with 3‐amino‐1‐propanols

Nitroarenes are reductively cyclized with 3‐amino‐1‐propanols in dioxane/H₂O in the presence of a ruthenium catalyst and tin(II) chloride dihydrate together with isopropanol to afford the corresponding quinolines. A reaction pathway involving initial reduction of nitroarenes to anilines, propanol group transfer from 3‐amino‐1‐propanols to anilines, N‐alkylation of anilines by 3‐anilino‐1‐propanols and heteroannulation of 1,3‐dianilinopropanes is proposed.     

Sequential actions of cobalt nanoparticles and palladium(II) catalysts: three-step one-pot synthesis of fenestranes from an enyne and an alkyne diester

A three-step one-pot synthesis of fenestranes from a readily available enyne and an alkyne diester has been carried out with cobalt nanoparticles and palladium(II) as catalysts.     

Nanophase segregation and water dynamics in the dendrion diblock copolymer formed from the Fréchet polyaryl ethereal dendrimer and linear PTFE

We propose a new material consisting of a dendrion copolymer formed from (a) a water-soluble dendritic polymer and (b) a hydrophobic backbone. Using molecular dynamics simulations techniques, we determine the structure and dynamics of the dendrion formed by second-generation Fréchet polyaryl ethereal dendrimer as the hydrophilic component and linear polytetrafluoroethylene (PTFE) as the hydrophobic polymer, with 5 and 10 wt % of water. We find that this material produces a well-developed nanoscale structure in which water forms a continuous nanophase, making this new family of compounds promising candidates for applications in fuel cell membranes. We find that the water molecules are incorporated into the dendrimer block of the copolymer to form a nanophase-segregated structure. The well-developed nanophase-segregated structures rendered by this material have characteristic dimensions of segregation ( approximately 30 Angstrom) and dendrimer conformational properties that are independent of water content. Calculations of water dynamics and proton transport in these nanophase-segregated structures indicate that the dendrion copolymer membrane with 10 wt % of water content has a water structure and transport properties equivalent to that of the hydrated Nafion membrane with 20 wt % of water content.     

Crucial role of three-center hydrogen bonding in a challenging chiral molecular recognition

The enantio-discrimination of beta-chiral primary ammonium ions is achieved by a rational approach that utilizes three-center (bifurcated) hydrogen bonding. The extraction experiments on various selected guests reveal that the bifurcated H-bonding plays a crucial role for the chiral discrimination. The X-ray data obtained for an inclusion complex substantiate such interactions. Using the bifurcated H-bonding, the chiral molecular recognition with our C(3)-symmetric tripodal oxazoline receptors is extended generally toward ammonium ions of alpha-, beta-, and alpha,beta-chiral amines. Simple molecular models, evoking the bifurcated H-bonding, explain the chiral discrimination modes.     

Dual effect of oxidative stress on NF-kappakB activation in HeLa cells

Reactive oxygen species (ROS) has been implicated as an inducer of NF-kappaB activity in numbers of cell types where exposure of cells to ROS such as H(2)O(2) leads to NF-kappaB activation. In contrast, exposure to oxidative stress in certain cell types induced reduction of tumor necrosis factor (TNF)- induced NF-kappaB activation. And various thiol-modifying agents including gold compounds and cyclopentenone prostaglandins inhibit NF-kappaB activation by blocking IkappaB kinase (IKK). To understand such conflicting effect of oxidative stress on NF- kappakB activation, HeLa cells were incubated with H(2)O(2) or diamide and TNF-induced expression of NF-kappaB reporter gene was measured. NF-kappaB activation was significantly blocked by these oxidizing agents, and the inhibition was accompanied with reduced nuclear NF-kappaB and inappropriate cytosolic IkappaB degradation. H(2)O(2) and diamide also inhibited IKK activation in HeLa and RAW 264.7 cells stimulated with TNF and lipopolysaccharide, respectively, and directly blocked IKK activity in vitro. In cells treated with H(2)O(2) alone, nuclear NF-kappaB was induced after 2 h without detectable degradation of cytosolic IkappaBalphaa or activation of IKK. Our results suggest that ROS has a dual effect on NF-kappaB activation in the same HeLa cells: it inhibits acute IKK-mediated NF-kappakB activation induced by inflammatory signals, while longer-term exposure to ROS induces NF-kappaB activity through an IKK-independent pathway.     

Synthesis and Structures of Titanosiloxane Cage Compounds

Reaction of (triphenylmethyl)silanetriol (1) with cyclopentadienyltitanium trichloride (CpTiCl₃) in the presence of triethylamine as a HCl scavenger gave both compounds of a partial open-cage type {[Ph₃CSiO(OH)]₃(Ph₃CSiO_3/2)(CpTiO_3/2)₄} (2) and cube type (Ph₃CSiO_3/2CpTiO_3/2)₄ (3). The 1:1 reaction of 1 and CpTiCl₃ in toluene solvent at reflux temperature for 3 d afforded compounds 2 (22%) and 3 (36%). When 1 is reacted with a 1.5 fold excess of CpTiCl₃ under the same conditions, compound 3 was obtained in high yield (81%) along with 2 in trace quantities. Compounds 2 and 3 were fully characterized by the analyses of ¹H, ¹³C, ²⁹Si NMR, IR, and FAB MS data. The solid-state structure of 3 was determined by a single crystal X-ray diffraction study. Compound 3 had shown to have catalytic activity for the oxidation of alkenes such as 1-octene, cyclooctene, and norbornene with t-butyl hydrogen peroxide. The effect of solvent was observed in this epoxidation reaction. The order of reactivity were decreased as follows: CHCl₃ > hexane THF.     

Efficient oxidation of benzylic alcohols with [hydroxy(tosyloxy)iodo]benzene under microwave irradiation

An efficient method for the oxidation of benzylic alcohols with [hydroxy(tosyloxy)iodo]benzene under solvent-free microwave irradiation conditions is described.     

Electron paramagnetic resonance study of partially oriented clay platelets intercalated with copper(II) 1,4,8,11-tetraazacyclotetradecane

Electron paramagnetic resonance (EPR) spectra of powder and oriented films of montmorillonite, hectorite, and saponite intercalated with [Cu(cyclam)](2+) (cyclam = 1,4,8,11-tetraazacyclotetradecane) exhibit three components: an orientation-dependent component without hyperfine features, an orientation-dependent component with hyperfine features, and an orientation-independent component without hyperfine feature. EPR spectra of [Cu(cyclam)](2+)-saponite, which exhibit only two components and the best resolved hyperfine features, were simulated. The spectra indicate that a large portion of the saponite platelets are inclined to the glass surface, although they tend to align with their basal planes parallel to the glass surface. The orientation-dependent spectra could be simulated by introducing a Gaussian distribution with a standard deviation of 20 degrees for the inclination angle. The standard deviation may be used as a disorder parameter for the microcrystals assembled on glass plates. Spectral simulation also shows that the CuN(4) plane of [Cu(cyclam)](2+) is parallel to the clay layers. EPR spectra of some other partially oriented systems are also discussed.