Efficient preparation of monohydrosilanes using palladium-catalyzed Si-C bond formation

The arylation of dihydrosilanes with aryl iodides or heteroaryl iodides in the presence of a palladium catalyst provides the corresponding monohydrosilanes in good to high yield. Moderate to good yields are obtained even in the presence of a variety of reactive functional groups, such as -NH2, -OH, or -CN, without their protection.     

Iron-catalyzed arylmagnesiation of aryl(alkyl)acetylenes in the presence of an N-heterocyclic carbene ligand

Addition of arylmagnesium bromides to aryl(alkyl)acetylenes proceeded in the presence of an iron catalyst and a N-heterocyclic carbene ligand to give high yields of the corresponding alkenylmagnesium reagents, which were transformed into tetrasubstituted alkenes by subsequent treatment with electrophiles. [reaction: see text]     

Extended x-ray absorption fine structure study of local structure and atomic correlations of tellurium nanoparticles

Extended x-ray absorption fine structure measurements were performed on trigonal tellurium (t-Te) and tellurium nanoparticles in very thin films. Twofold coordinated chains, much like those in t-Te, exist even in the nanoparticles, but covalent bonds or intrachain interactions are stronger than those of t-Te as shown by a shorter bond length and higher Einstein temperature. The interchain coordination number of the nanoparticles is about half that of t-Te, suggesting reduction of interchain interactions.     

Advanced dress-up chiral columns: New removable chiral stationary phases for enantioseparation of chiral carboxylic acids

This paper describes the preparation of new dress-up columns featuring reproducibly removable and replaceable chiral stationary phases. After synthesizing perfluroalkylated quinine and quinidine derivatives as chiral stationary phase compounds (F-CSPs), we adsorbed them reversibly onto a fluorous LC column through pumping of their solutions. Using this dress-up chiral column and fluorophobic elution of aqueous ammonium formate/MeOH mixtures, we could enantioseparate four racemic N-acetyl amino acids, dichlorprop, and sixteen fluorescent 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC)-derivatized amino acids. Dressing and undressing of the coated F-CSPs could be controlled by varying the fluorophilicity and fluorophobicity of the eluent. The relative standard deviations of the retention times, the retention factors, the number of theoretical plates, the enantioseparation factors, and the resolutions of each of four preparations of such dress-up columns were all less than or equal to 5.26% (from 20 repeated analyses); the reproducibilities from four different preparations were all less than or equal to 10.6%. These columns also facilitated highly sensitive and selective analyses of AQC-amino acids when detected using LC–MS/MS.     

Tandem oxidation/bromination of ethyl aromatics to α,α-dibromoacetophenones with molecular oxygen under visible light irradiation

The facile synthesis of α,α-dibromoacetophenones from ethyl-substituted aromatics by aerobic photooxidation has been developed. This synthetic method achieves oxidative dibromination of aromatic ethyl groups by using inexpensive and easily handled bromine sources, harmless visible light and molecular oxygen.     

Aqua cadmium cyanide coordination polymer with nitronyl nitroxide radical

A new three-dimensional diamagnetic metal nitronyl nitroxide radical coordination polymer with an aqua cadmium cyanide framework Cd(NIT4py)(H₂O)Cd(CN)₄·H₂O 1, was synthesized. X-ray crystallography reveals that the structure consists of 3D aqua cadmium cyanide built up by octahedral Cd^II coordinating to NIT4py and tetrahedral Cd^II (CN)₄ units. Magnetic measurements show that the χ_mT values are nearly constant at higher temperature. The lower χ_mT values at lower temperature are related to intermolecular antiferromagnetic interactions of the radicals, which arise due to the hydrogen bonded network (T_N = 21 K).     

Cross coupling between sp3-carbon and sp3-carbon using a diborylmethane derivative at room temperature

A novel example of the Suzuki-Miyaura cross-coupling reaction between sp(3)-carbon and sp(3)-carbon is described. The reaction of a diborylmethane derivative with allyl halides or benzyl halides proceeded efficiently in the presence of appropriate Pd-catalysts at room temperature. The present approaches provide functionalized homoallylboronates and alkylboronates with excellent regio- and chemoselectivities.     

Theoretical study of dynamic electron-spin-polarization via the doublet-quartet quantum-mixed state (II). Population transfer and magnetic field dependence of the spin polarization

The population transfer to the spin-sublevels of the unique quartet (S = 3/2) high-spin state of the strongly exchange-coupled (SC) radical-triplet pair (for example, an Acceptor-Donor-Radical triad (A-D-R)) via a doublet-quartet quantum-mixed (QM) state is theoretically investigated by a stochastic Liouville equation. In this work, we have treated the loss of the quantum coherence (de-coherence) due to the de-phasing during the population transfer and neglected the effect of other de-coherence mechanisms. The dependences on the magnitude of the exchange coupling or the fine-structure parameter of the QM state are investigated. The dependence on the velocity of the population transfer (by the electron transfer or the energy-transfer) from the QM state to the SC quartet state is also clarified. It is revealed that the de-coherence during the population transfer mainly originates from the fine-structure term of the QM state in the doublet-triplet exchange coupled systems. This de-coherence leads to the unique dynamic electron polarization (DEP) on the high-field spin sublevels of the SC state, which is similar to the unique DEP pattern of the photo-excited triplet states of the reaction centers of photosystems I and II. The magnetic field dependence of the population transfer leading to the populations of the spin-sublevels of the SC states is also calculated. The possibility of the control of energy transport, spin transport and information technology by using the QM state is discussed based on these results. The knowledge obtained in this work is useful in the spin dynamics of any doublet-triplet exchange coupled systems.     

Existence of a ground state and scattering for a nonlinear Schrödinger equation with critical growth

We study the energy-critical focusing nonlinear Schrödinger equation with an energy-subcritical perturbation. We show the existence of a ground state in the four or higher dimensions. Moreover, we give a sufficient and necessary condition for a solution to scatter, in the spirit of Kenig and Merle (Invent Math 166:645–675, 2006).     

Gr?bner bases of contraction ideals

We investigate Gr?bner bases of contraction ideals under monomial homomorphisms. As an application, we generalize the result of Aoki?CHibi?COhsugi?CTakemura and Ohsugi?CHibi for toric ideals of nested configurations.