Room-Temperature,Metal-Free,and One-Pot Preparation of 2H-Indazoles through a Mills Reaction and Cyclization Sequence

The Mills reaction and cyclization of readily available 2-aminobenzyl alcohols and nitrosobenzenes using thionyl bromide provided 2H-indazoles in up to 88 % yields. In the metal-free process, acetic acid played a crucial role for the both Mills reaction and cyclization. A brominated 2H-indazole could also be obtained through the one-pot sequence.     

Supramolecular Sensor for Astringent Procyanidin C1: Fluorescent Artificial Tongue for Wine Components

An artificial tongue that detects astringent components for a comprehensive evaluation of taste has not been established to date. Herein, we first propose fluorescent polythiophene (PT) derivatives ( S1 – S3 ) modified with 3-pyridinium boronic acid as supramolecular chemosensors for wine components including astringent procyanidin C1. After numerous attempts for the synthetic conditions, more than 95 mol % of the PT unit was modified with the pyridinium boronic acid moiety. To evaluate the PT derivatives as chemosensors of the artificial tongue, qualitative and quantitative analyses were performed with four types of wine components (i.e., sweet, sour, bitter, and astringent tastes) in combination with pattern recognition models. Notably, procyanidin C1 in the actual wine sample was successfully detected in a quantitative manner. In other words, we have established an authentic artificial tongue using PT based supramolecular chemosensors.     

Design and synthesis of spiro bis(1,2,3-triazolium) salts as chiral ionic liquids

Room temperature chiral spiro ionic liquids 1 and 2 based on 1,2,3-triazolium salts, were synthesized via an intramolecular double Huisgen reaction. The preparation of the enantiomerically pure spiro triazolium salts was achieved by resolution by HPLC using a chiral stationary phase column and subsequent N-dialkylations of spiro triazoles 6 and 10.     

Chiral bifunctional organocatalysts bearing a 1,3-propanediamine unit for the aza-MBH reaction

The introduction of a 1,3-propanediamine unit at the 3-position of (S)-BINOL using a methylene spacer led to the formation of a chiral bifunctional organocatalyst for the aza-Morita–Baylis–Hillman (aza-MBH) reaction. The organocatalyst 1k mediated aza-MBH transformations with high chemical yields and with up to 82% ee.     

Deprotection of dithioacetals with 30% hydrogen peroxide catalyzed by tantalum(V) chloride–sodium iodide or niobium(V) chloride–sodium iodide

The reaction of dithioacetals with 30% hydrogen peroxide in the presence of catalytic amounts of tantalum(V) and iodide ion effectively produced carbonyl compounds in high yields. Dithioacetals also can be deprotected using the niobium(V) catalyzed oxidation of iodide ion by hydrogen peroxide under mild conditions.     

DFT Study of a 5‐endo‐trig‐Type Cyclization of 3‐Alkenoic Acids by Using Pd–Spiro‐bis(isoxazoline) as Catalyst: Importance of the Rigid Spiro Framework for Both Selectivity and Reactivity

The reaction pathway of an enantioselective 5‐endo‐trig‐type cyclization of 3‐alkenoic acids catalyzed by a chiral palladium–spiro‐bis(isoxazoline) complex, Pd–SPRIX, has been studied by density functional theory calculations. The most plausible pathway involves intramolecular nucleophilic attack of the carboxylate moiety on the C?C double bond activated by Pd–SPRIX and β‐H elimination from the resulting organopalladium intermediate. The enantioselectivity was determined in the cyclization step through the formation of a π‐olefin complex, in which one of the two enantiofaces of the olefin moiety was selected. The β‐H elimination occurs via a seven‐membered cyclic structure in which the acetate ligand plays a key role in lowering the activation barrier of the transition state. In the elimination step, the SPRIX ligand was found to behave as a monodentate ligand due to the hemilability of one of the isoxazoline units thereby facilitating the elimination. Natural population analysis of this pathway showed that the more weakly electron‐donating SPRIX ligand, compared with the bis(oxazoline) ligand, BOX, facilitated the formation of the π‐olefin complex intermediate, leading to a smaller overall activation energy and a higher reactivity of the Pd–SPRIX catalyst.     

The effects of oxidative reaction on ionic permeabilities through polypeptide membranes containing –SH groups in the side chains

The effects of the oxidative reaction on the ionic permeabilities through polypeptide membranes containing thiol groups in the side chains were investigated. Membranes were derived from poly(glutamyl-cysteine) (PGC) containing 12% (in mol %) of ? SH groups in the side chains, and from poly(L-cysteine) (PlCys) containing 26% of thiol groups in the side chains, respectively. On the basis of the polarographic analysis, it can be estimated that more than 80% of ? SH groups in the membranes could be oxidized by using 10 mM solution of iodine. The membrane potentials across the PGC membrane were increased by the iodine oxidation, indicating that ? SH groups of PGC were converted to highly dissociable groups, i.e., sulfonic acid derivatives. The decrease in the ionic permeabilities through the PGC membrane by the oxidation, therefore, was attributed to the decrease in ionic solubility into the membrane owing to the increase in fixed charge density of the membrane (Donnan exclusion effect). On the other hand, no influence of the oxidation on the membrane potentials of the PCys membrane suggests the possibility of oxidative S-S cross linking in the membrane. The oxidation-induced permeability decrease of the PCys membrane could be explained in terms of the decrease in ionic diffusibility associated with the formation of the side chain cross linkings between ? SH groups in the membrane.     

Signal measurement system for intra-body communication using optical isolation method

In this paper, we describe an induced signal measurement on the human body for developing a high-performance transceiver of an intra-body communication system. It is important to isolate awearable transceiver from an electrical instrument for precise measurement. We have developed a probe system using an optical isolation method including a laser diode, photo-diode, and optical fiber. The probe system can be successfully applied to the precise measurement of a receiving signal power at a wearable transceiver. We verify that the experimental results agree with the simulation results based on our previous channel model of intra-body communication.     

Electronic structures in coupled two quantum dots by 3D-mesh Hartree-Fock-Kohn-Sham calculation

To study the electronic structures of quantum dots in the framework of self-interaction-free including three dimensional effects, we adopt the theory of nonlocal effective potential introduced by Kohn and Sham [#!ks65!#]. For utilizing the advantageous point of the real space (3D) mesh method to solve the original nonlinear and nonlocal Hartree-Fock-Kohn-Sham (HFKS)-equation, we introduce a linearization of the equation in the local form by introducing the local Coulomb potentials which depend on explicitly the two single particle states. In practice, for solving the local form HFKS-equation, we use the Car-Parrinello-like relaxation method and the Coulomb potentials are obtained by solving the Poisson equation under proper boundary conditions. Firstly the observed energy gap between triplet- and singlet-states of N = 4 in DBS [#!tarucha96!#] is discussed to reproduce the addition energies and chemical potentials depending the magnetic field. Next the coupling between two-quantum dots in TBS [#!aht97!#] is studied by adding the square barrier between two dots. The spin-degeneracy [#!aht97!#] measured in gate-voltage depending on magnetic field is well reproduced in the limit of small mismatch. Finally, the electronic states in the ring structure are calculated and discussed how the ring size and magnetic field affect to the structures. Received 30 November 2000