Transition-Metal Free Catalytic Synthesis of Trifluoromethyl Indolines by [4+1] Cycloaddition of Trifluoromethyl Benzoxazinones with Sulfur Ylides

Stereoselective catalytic synthesis of 3-trifluoromethyl indolines through the [4+1] cycloaddition of benzoxazinones and sulfur ylides in a transition-metal-free manner was developed. In the presence of a catalytic amount of sodium hydride, aza-ortho-quinone methide intermediates were formed from trifluoromethyl benzoxazinones through decarboxylation after the first nucleophilic attack of sulfur ylides, which progressed to a second nucleophilic attack of sulfur ylides, resulting in the [4+1] cycloaddition. The key for this catalytic transformation is the dual attack of sulfur ylides on substrates. This unique transition-metal-free protocol is applicable to the synthesis of non-fluorinated vinyl-, ethynyl- or methyl-substituted indolines. The synthesis of 3-trifluoromethyl indoles was also achieved described under stoichiometric conditions.     

Surgical effects on soft tissue produced by a 405-nm violet diode laser in vivo

This study evaluated the surgical performance of a 405-nm diode laser in vivo, using living rat liver tissue. Tissue was incised by irradiation with the laser at low output power ranging from 1 W (722 W/cm²) to 3 W (2165 W/cm²) on a manual control at a rate of 1 mm/s. As a control, incisions using a stainless scalpel were compared. Immediately after operation, the surface of the incisions was macroscopically observed and histopathologically evaluated by microscopy. Laser-ablated liver tissue was smooth with observable signs of remnant carbonization and easily acquired hemostasis. The thickness of the denatured layer increased in proportion to the output power; the coagulation layer did not thicken accordingly. Bleeding could not be stopped for tissues incised with the stainless scalpel. The 405-nm diode laser thus proved to be effective for ablating soft tissue with high hemostatic ability at low power.     

Nickel-catalyzed intermolecular coupling of 1,3-dienes and aldehydes via transmetalation of nickelacycles with diisobutylaluminum acetylacetonate

Intermolecular coupling reactions of 1,3-dienes and aldehydes via transmetalation of nickelacycle intermediate with (i)Bu(2)Al-acac were investigated. In the reactions, a linear adduct or a branched adduct was produced, depending upon the nature of 1,3-dienes and aldehydes, via two nickelacycles that were relatively stable among the four possible nickelacycles because of the equilibrium with pi-allynickel forms.     

Single-molecule reaction and characterization by vibrational excitation

Controlled chemical reaction of single trans-2-butene molecules on the Pd(110) surface was realized by dosing tunneling electrons from the tip of a scanning tunneling microscope at 4.7 K. The reaction product was identified as a 1,3-butadiene molecule by inelastic electron tunneling spectroscopy. Threshold voltage for the reaction is approximately 365 mV, which coincides with the vibrational excitation of the C-H stretching mode. The reaction was ascertained to be caused by C-H bond dissociation by multiple vibrational excitations of the C-H stretching mode via inelastic electron tunneling process.     

Charge transport study on single crystals of β-LiAl

Charge transport properties of β-LiAl were studied in the composition range of 48.0–50.2 at.% Li. Measurements were made on single crystal samples and down to the liquid He temperature. The resistivity changes linearly with temperature above 125 K, with a thermal coefficient of 72–95nΩ cm K^?1. The Matthiessen law was obeyed very well. A component dependent on temperature, which was described by the Grüneisen formula, is insensitive to a change of the chemical composition. On the other hand, the residual resistivity depends largely on the composition and contributes up to 58% of the total resistivity in Li_0.498. It is chiefly due to the substituted Li atoms on the Al sublattice.