Palladium-catalyzed multiple arylation of thiophenes

Secondary 2-thiophenecarboxamides efficiently undergo unique triarylation accompanied by formal decarbamoylation under palladium catalysis. 3-Substituted thiophenes, especially having an electron-withdrawing group, can also be triarylated.     

Selective removal of tetrahydropyranyl ethers in the presence of t-butyldimethylsilyl ethers

Dimethylaluminiun chloride has been found to cleave THP ethers selectively without any removal of t-butyldimethylsilyl ethers     

Selective absorption

Summary Some organic acids, alcohol and amine which have an asymmetric carbon atom were used for an investigation of asymmetric absorption on wool. Racemic mixture of hydratropic acid, mandelic acid andα-phenethylamine have shown the selective absorption on wool from their aqueous and alcoholic aqueous solutions and S-form of their diastereoisomers preferentially absorbed on wool. According to the results we obtained so far, it is concluded that the preferential absorption strongly depends on the configuration of the substance of which wool is composed.     

Formation of cyclic organosilicon compounds via organopolysilyl anions starting from methoxymethyldisilanes. A mechanistic study

In the presence of a catalytic amount of sodium methoxide, sym-dimethoxytetramethyldisilane was converted into α,ω-dimethoxypermethylpolysilanes, MeO(SiMe₂)_nOMe where n ? 3, at room temperature. On the other hand, similar treatment of the disilane in THF solution gave cyclic polysilanes, (Me₂Si)_n where n = 5–7. Decomposition of the disilane in the presence of diphenylacetylene afforded a trisilacyclopentene derivative under similar conditions. This compound was obtained also by the reaction between α,ω-dimethoxypermethylpolysilanes and diphenylacetylene in the presence of sodium methoxide. These cyclic products most likely were formed via permethyl polysilyl anion intermediates derived from α,ω-dimethoxypermethylpolysilanes. Also, the formation of α,ω-dimethoxypermethylpolysilanes could be elucidated in terms of the mechanism involving the base-assisted, concerted nucleophilic substitution or stepwise substitution by silyl anions, rather than the successive dimethylsilylene (Me₂Si:) insertion reaction.     

Real-time charge oscillation between monomers in a dimeric system associated with intermolecular vibration induced by an ultrashort pulse

Ultrafast charge resonant (CR) dynamics between two molecules in a dimer system has been studied theoretically and experimentally using 6-fs laser pulses and a thin film of amorphous-phase phthalocyanine tin(IV) dichloride (SnPc). The modulation of the absorbance change in the bleaching spectral range of the CR absorption band was analyzed to obtain the amount of charge resonantly transferred back and forth by a dimeric vibration induced by photoexcitation. The modulation can be explained in terms of a periodic change in the cross section and a periodic energy shift, where both are induced by the change in the overlap integral caused by the accordion-type intermolecular vibration. The associated change in distance between two molecules with the intermolecular vibration was estimated to be 0.09 A, which corresponds to 2.5% of the mean distance between the two SnPc molecules in the dimeric system.     

syn-selective direct catalytic asymmetric Mannich-type reactions of hydroxyketones using Y{N(SiMe3)2}3/linked-BINOL complexes

[reaction, structure: see text] Chiral Y{N(SiMe3)2}3/linked-BINOL catalyst generated Y-enolate in situ from various hydroxyketones (R2 = aryl, heteroaryl). Beta-amino-alpha-hydroxy ketones (R1 = aryl, heteroaryl, alkenyl) were obtained syn-selectively (up to 96/4) in high ee (up to 98%) and good yield (up to 98% yield).     

Electric conductivities of 1:1 electrolytes in liquid methanol along the liquid-vapor coexistence curve up to the critical temperature. I. NaCl, KCl, and CsCl solutions

The molar conductivities Lambda of NaCl, KCl, and CsCl in liquid methanol were measured in the concentration range of (0.3-2.0) x 10(-3) mol dm(-3) and the temperature range of 60-240 degrees C along the liquid-vapor coexistence curve. The temperature range corresponds to the solvent density range of (2.78-1.55)rhoc, where rhoc = 0.2756 g cm(-3) is the critical density of methanol. The concentration dependence of Lambda at each temperature and density (pressure) has been analyzed by the Fuoss-Chen-Justice equation to obtain the limiting molar conductivity Lambda0 and the molar association constant KA. For all the electrolytes studied, Lambda0 increased almost linearly with decreasing density at densities above 2.0rhoc, while the opposite tendency was observed at lower densities. The relative contribution of the nonhydrodynamic effect on the translational friction coefficient zeta was estimated in terms of Deltazeta/zeta, where the residual friction coefficient Deltazeta is the difference between zeta and the Stokes friction coefficient zetaS. At densities above 2.0rhoc, Deltazeta/zeta increased with decreasing density though zeta and Deltazeta decrease, and the tendencies are common for all the ions studied. The density dependences of zeta and Deltazeta/zeta were explained well by the Hubbard-Onsager (HO) dielectric friction theory based on the sphere-in-continuum model. At densities below 2.0rhoc, however, the experimental results cannot be explained by the HO theory.