Organic reactions mediated by electrochemically generated ArS+

Low-temperature electrochemical oxidation of ArSSAr was carried out to generate a pool of "ArS(+)". Spectroscopic studies ((1)H NMR and CSI-MS) of the resulting solution revealed the accumulation of ArS(ArSSAr)(+). The resulting "ArS(+)" pool reacted with alkenes and alkynes to give diarylthio-substituted products. The "ArS(+)" pool rapidly reacted with thioacetals to give the corresponding alkoxycarbenium ion pools, which reacted with various carbon nucleophiles (indirect cation pool method). The reaction of the alkoxycarbenium ion pools with stilbene derivatives in the presence of ArSSAr gave thiochroman derivatives. In addition to such stoichiometric reactions, a catalytic amount of "ArS(+)" serves as an initiator and a chain carrier of some cationic chain reactions involving intramolecular carbon-carbon bond formation. In situ generation of "ArS(+)" by electrochemical oxidation of ArSSAr with a catalytic amount of electricity in the presence of a substrate is also effective for such cationic chain reactions.     

Protonic Conduction and O-H Bonding State in Phosphate Glasses

Abstract

Protons in alkaline-earth phosphate glasses give much higher mobility than those in silicate glasses. This is caused by the difference in O-H bonding state. Protons in P-OH form a strong hydrogen bonding with oxygen anion, resulting in formation of weak O-H bond.

The electrical conductivity of the glasses is proportional to the square of the proton concentration. The activation energy for the conduction is related to ν_OH, peak wavenumber of infrared absorption band (around～3000 cm^?1), due to fundamental O-H stretching vibration. The mobility of protons increases with decreasing ν_OH, which depends on the species of ions included in the phosphate glasses.     

A theoretical study on the ionization of OCS with an analysis of vibrational structures of the photoelectron spectrum

 Ab initio calculations have been performed to study the molecular structures and vibrational levels of the four low-lying ionic states (1, 2²Π, and 1, 2²Σ⁺) of carbonyl sulfide. The global regions of the potential-energy surfaces have been obtained by multireference single and double excitation configuration interaction calculations. Vibrational calculations using explicit vibrational Hamiltonians have been used for vibrational analysis. The equilibrium molecular structures and a vibrational analysis of the four ionic states are presented. The theoretical ionization intensity curves including the vibrational structures of the ionic states are also presented and are compared with the photoelectron spectrum. Received: 20 January 2001 / Accepted: 22 August 2001 / Published online: 30 October 2001     

Hyperfine structure of the electron spin resonance of phosphorus-doped Si nanocrystals

Electronic states of P donors in Si nanocrystals (nc-Si) embedded in insulating glass matrices have been studied by electron spin resonance. Doping of P donors into nc-Si was demonstrated by the observation of optical absorption in the infrared region due to intraconduction band transitions. P hyperfine structure (hfs) was successfully observed at low temperatures. The observed splitting of the hfs was found to be much larger than that of the bulk Si:P and depended strongly on the size of nc-Si. The observed strong size dependence indicates that the enhancement of the hyperfine splitting is caused by the quantum confinement of P donors in nc-Si.     

Synthetic macrocyclic ligands. III. Synthesis of a quinone-hydroquinone redox system incorporated with complexing ability toward cations

Two quinones bridged with a polyether chain and the corresponding hydroquinones were synthesized, and their redox reaction and complexations with sodium and potassium ions were observed.     

Chiral phosphinooxazolidine ligands for palladium- and platinum-catalyzed asymmetric Diels-Alder reactions

Cationic palladium (Pd)- and platinum (Pt)-phosphinooxazolidine catalysts 13a-c, 15a-d, 17a-c, and 19a-c were prepared from phosphinooxazolidine ligands 1-3, MCl(2) (M = Pd and Pt), and counterions, and the activities of the catalysts in the asymmetric Diels-Alder (DA) reactions of cyclic or acyclic dienes with imide dienophiles were investigated. These catalysts demonstrated high levels of catalytic activity. The cationic Pd-POZ complex 13c provided particularly excellent enantioselectivity (98% ee) in the DA reactions of cyclopentadiene with acryloyl-, crotonyl-, and fumaroyl-1,3-oxazolidin-2-ones (20a-c).     

On the Eigenstates of the Elliptic Calogero–Moser Model

It is known that the trigonometric Calogero–Sutherland model is obtained by the trigonometric limit (–1) of the elliptic Calogero–Moser model, where (1, ) is a basic period of the elliptic function. We show that for all square-integrable eigenstates and eigenvalues of the Hamiltonian of the Calogero–Sutherland model, if exp(2–1) is small enough then there exist square-integrable eigenstates and eigenvalues of the Hamiltonian of the elliptic Calogero–Moser model which converge to the ones of the Calogero–Sutherland model for the 2-particle and the coupling constant l is positive integer cases and the 3-particle and l=1 case. In other words, we justify the regular perturbation with respect to the parameter exp(2–1). With some assumptions, we show analogous results for N-particle and l is positive integer cases.     

Time‐resolved x‐ray fluorescence for monitoring the intake of mineral nutrients in living plants

We have applied a time‐resolved means of measurement for studying living plants. The intake of mineral nutrients in a living plant such as stevia has been observed by this measuring instrument. A solution containing K, Ca, Mn, Fe, Cu, and Zn compounds was used as the mineral nutrient solution. The concentrations of the standard solutions were specifically chosen to obtain optimal intensities of the x‐ray peaks. The time dependence of the x‐ray fluorescence (XRF) intensity showed specific intake processes depending on the type of element. In addition, the experimental results suggest differences in the translocation of each element in the stevia stem. We conclude that time‐resolved XRF is a powerful technique for studying living plants. Copyright © 2007 John Wiley & Sons, Ltd.     

Novel and efficient chiral sulfideoxathiane ligands for palladium-catalyzed asymmetric allylic alkylation

Easily prepared, chiral sulfideoxathiane ligands are described which give excellent enantioselectivity (up to 99% ee) in the Pd-catalyzed allylic alkylation of 1,3-diphenyl-2-propenyl acetate with a range of alkyl malonate nucleophiles.