Cobalt-mediated cross-coupling reactions of primary and secondary alkyl halides with 1-(trimethylsilyl)ethenyl- and 2-trimethylsilylethynylmagnesium reagents

[reaction: see text] This paper describes cobalt-mediated cross-coupling reactions of alkyl halides with 1-(trimethylsilyl)ethenylmagnesium bromide and 2-(trimethylsilyl)ethynylmagnesium bromide, respectively. The cobalt system allows for employing secondary as well as primary alkyl halides as the substrates. The reactions offer facile formations of alkyl-alkenyl and alkyl-alkynyl bonds. The reaction mechanism would include single-electron transfer from a cobalt complex to alkyl halide to generate the corresponding alkyl radical. The cobalt system thus enables sequential radical cyclization/alkenylation and cyclization/alkynylation reactions of 6-halo-1-hexene derivatives.     

Phosphine‐Catalyzed anti‐Carboboration of Alkynoates with 9‐BBN‐Based 1,1‐Diborylalkanes: Synthesis and Use of Multisubstituted γ‐Borylallylboranes

Trialkylphosphine organocatalysis has enabled the regioselective anti‐carboboration of alkynoates with 9‐BBN‐based 1,1‐diborylalkanes to produce secondary allylboranes with β‐alkoxycarbonyl and γ‐boryl substituents. The utility of the densely functionalized allylboranes was demonstrated by the highly diastereoselective allylation of N‐(trimethylsilyl)aldimines to produce homoallylamines containing tertiary allylborane and acrylate moieties.     

EXAFS measurements for liquid As2Se3 at high temperatures and pressures

Extended X-ray absorption fine structure (EXAFS) spectra from liquid As₂Se₃ around both the As and Se K-edges in the temperature-pressure range up to 1400°C and about 60 bar were measured. For the EXAFS measurements, a new type of high pressure vessel and a sample cell of own design made of polycrystalline sapphire were developed. Distinct EXAFS oscillations were obtained even at 1400°C. When the semiconductor-to-metal transition occurs at about 1000°C, the local environment around a central As atoms is substantially changes and a new As neighbor site is induced.     

Synthesis of benzylpalladium complexes through C-O bond cleavage of benzylic carboxylates: Development of a novel palladium-catalyzed benzylation of olefins

Benzylic carboxylates were found to react with Pd(0) complexes bearing tertiary phosphines to give benzylpalladium(II) carboxylate complexes with cleavage of the benzyl-oxygen bond. The benzylpalladium complexes having the trifluoroacetato ligand react with olefins such as ethyl acrylate to give olefin benzylation products. On the basis of these studies a novel palladium-catalyzed benzylation of olefins was developed without using organic halides as the starting materials. The method has another advantage of requiring no base as in the conventional Mizoroki-Heck process using organic halides. The catalytic cycle is proposed to be constituted of elementary processes of (a) oxidative addition of a benzyl carboxylate with C-O bond cleavage to a Pd(0) complex to give a benzylpalladium carboxylate, (b) olefin insertion into the benzylpalladium bond to give an alkylpalladium complex, and (c) β-H abstraction to liberate the benzylated olefin.     

N-heterocyclic carbene ligands in cobalt-catalyzed sequential cyclization/cross-coupling reactions of 6-halo-1-hexene derivatives with Grignard reagents

[reaction: see text] N-Heterocyclic carbene/cobalt systems effectively catalyze sequential cyclization/cross-coupling reactions of 6-halo-1-hexene derivatives with trialkylsilylmethyl and 1-alkynyl Grignard reagents, which phosphine and amine ligands did not promote.     

Luminance-Type Additive Mechanism Produces Shading

It has been reported that the luminance mechanism mediates shadow perception of binary images. We evaluated the luminance additivity law to determine whether shading, which is produced by gradual intensity changes, is mediated by luminance or brightness using pictures with tones: two still lives and a painting. They were depicted by two colors-a reference color and a test color. The reference color was white with a constant luminance profile, and the test color was a mixture of red and green in various proportions. The observer’s task was to adjust the luminance of the test color in order that the impression of depth due to shading just disappeared (shading disappearance setting), where the intensity that produced the shading supposed to be equated between the test and the reference colors. The results show that the luminance additivity law holds for shading disappearance settings. This suggests that shading perception is based on luminance or a luminance-type additive mechanism as well as shadow.     

Coherence effect on decryption characteristics in message modulation type chaos secure communication systems using fiber-optic ring resonators

We numerically investigated the dependence of the decryption characteristics in a message modulation type chaos secure communication system using optical fiber ring resonators (OFRRs) on the coherence condition of carrier light. Since the output dynamics of OFRRs were formed on the basis of interference phenomenon among the circulated components in OFRRs, the coherence condition of input light affected inherently the OFRR output dynamics, resulting in the decryption characteristics. It was found that the decryption characteristics degraded as coherence length increased, i.e., as the spectral width of the input light decreased. The decryption characteristics also grew worse as the parameter differences between the transmitter and the receiver became larger.     

Potential-modulated fluorescence spectroscopy of the membrane potential-sensitive dye di-4-ANEPPS at the 1,2-dichloroethane/water interface

The spectrofluorometric behavior of a membrane potential-sensitive dye, 1-(3-sulfonatopropyl)-4-[β-{2-(di-N-butylamino)-6-naphthyl}vinyl]pyridinium betaine (di-4-ANEPPS), at the polarized 1,2-dichloroethane/water interface was studied by means of potential-modulated fluorescence (PMF) spectroscopy. The results, combined with those from cyclic and alternating current voltammetry, clearly suggested that the dye adsorbed at the interface underwent a reorientation with increasing the interfacial potential, giving a well-developed PMF response as well as a voltammetric response. In addition to the PMF response, another PMF response was observed by addition of dilauroyl phosphatidylcholine (DLPC). This additional response was well explained in terms of a reorientation of di-4-ANEPPS at the interface, which would be induced by the potential-dependent desorption of DLPC from the interface. Thus, the present study supported the reorientation/solvatochromic mechanism for the membrane potential-sensitive dye rather than the electrochromic mechanism.     

Synthesis of conjugated allenes through copper-catalyzed γ-selective and stereospecific coupling between propargylic phosphates and aryl- or alkenylboronates

A Cu-catalyzed γ-selective coupling reaction between propargylic phosphates and aryl- or alkenylboronates afforded aryl- or alkenyl-conjugated allenes. The reaction showed excellent functional group compatibility in both the propargylic substrates and the boronates. The reaction of an enantioenriched propargylic phosphate proceeded with excellent chirality transfer with 1,3-anti stereochemistry to give axially chiral aryl- and alkenylallenes.