Stereodivergent Synthesis of Arylcyclopropylamines by Sequential CH Borylation and Suzuki–Miyaura Coupling

A step‐economical and stereodivergent synthesis of privileged 2‐arylcyclopropylamines (ACPAs) through a C(sp³)? H borylation and Suzuki–Miyaura coupling sequence has been developed. The iridium‐catalyzed C? H borylation of N‐cyclopropylpivalamide proceeds with cis selectivity. The subsequent B‐cyclopropyl Suzuki–Miyaura coupling catalyzed by [PdCl₂(dppf)]/Ag₂O proceeds with retention of configuration at the carbon center bearing the Bpin group, while epimerization at the nitrogen‐bound carbon atoms of both the starting materials and products is observed under the reaction conditions. This epimerization is, however, suppressed in the presence of O₂. The present new ACPA synthesis results in not only a significant reduction in the steps required for making ACPA derivatives, but also the ability to access either isomer (cis or trans) by simply changing the atmosphere (N₂ or O₂) in the coupling stage.     

UV-induced vertical alignment liquid crystal cell with two species of monomers having vertical-alignment-induced side-chain group and phenanthrene group

We propose the method for formation of the vertical alignment polymer film by polymerisation of the monomers being dissolved in the liquid crystal (LC) material. For obtaining the vertical alignment, combination of the two monomers, 4-(4?-octyloxy-biphenyl-4-yloxy)-butyl ester (AOBBE) and 2,7-dimethacryloyl-oxy-phenanthrene (DMAPhen), was found to be useful.

The monomer DMAPhen initiates the polymerisation under UV light exposure, and the AOBBE unit induces the vertical alignment without generating any alignment defects. The monomer DMAPhen is useful for maintaining the high voltage holding ratio and low residual direct current voltage after UV light exposure because the molecules of DMAPhen do not remain in the LC layer.     

Electrical conductivity and chemical diffusion in Perovskite-type proton conductors in H2-H2O gas mixtures

The electrical conductivities of SrZr_0.9Y_0.1O_3-δ (SZY10) and BaCe_0.95Y_0.05O_3-δ(BCY5) were measured as a function of hydrogen partial pressure P(H₂), oxygen partial pressure P(O₂), steam partial pressure P(H₂O) and temperature. Their relaxation processes were analyzed using the solution of Fick's diffusion equation to determine the chemical diffusion coefficients and surface reaction rate constants. There were the differences in chemical relaxation kinetics and the conductivity dependence on P(H₂O) between the both oxides. The chemical diffusion coefficients depend on temperature but are essentially independent of P(H₂), P(O₂) and P(H₂O). The ambipolar diffusion treatment can explain the temperature dependence of chemical diffusion coefficients quantitatively. The chemical diffusion coefficients of SZY10 is one or two order of magnitude smaller than those of BCY5 at low temperature. The sluggish conductivity relaxation in SZY10 was due to considerably small oxygen vacancy diffusion coefficients at low temperatures. The total conductivity depends on P(H₂O) in the case of SZY10, but not for BCY5. This different dependence on P(H₂O) is caused by the difference in the ratio between proton mobility and oxide-ion mobility.     

Collagen fibers evaluation after rhBMP-2 insertion in critical-sized defects

The objective of this investigation was to assess the quantity of collagen fibers with different dosages of recombinant human bone morphogenetic protein, type 2 (rhBMP-2) associated with two different carriers, monoolein and poloxamer gels, in critical bone defects created in the calvaria of Wistar rats. Forty male adult Wistar rats were divided into eight groups of 5 animals each—group I: critical bone defect with application of 1 μg of rhBMP-2 combined with monoolein gel; group II: 3 μg of rhBMP-2 combined with monoolein gel; group III: 7 μg of rhBMP-2 combined with monoolein gel; group IV: 1 μg of rhBMP-2 combined with poloxamer gel; group V: 3 μg of rhBMP-2 combined with poloxamer gel; group VI: 7 μg of rhBMP-2 combined with poloxamer gel; group VII: monoolein gel only and group VIII: poloxamer gel only. A critical-sized defect of 6 mm diameter was produced in the left parietal bone using a surgical round bur and a high-speed micromotor. The bone defects were filled according to the group that animals belonged and after two weeks the rats were perfused and their calvarial bones were removed for histological processing, and collagen fibers quantification. Differences among the eight groups were statistically analyzed by Anova and Bonferroni test (p < 0.05). The results did not show statistical difference between the groups, in exception, between the comparisons II and III. According to the experimental methodology used in this research, it was observed, in a general way, a qualitative inverse relationship between collagen fibers presence and rhBMP-2 quantity inserted in the critical bone defect, associated or not to a material carrier.     

Recent Progress in the Synthesis of the Monocarba-closo-dodecaborate(−) Anions

This Concept article focuses on the rapid growth in studies of the chemistry of the monocarba-closo-dodecaborate(−) anion (C1 carborane anion). As one of the most stable anions known, the C1 carborane anion has been useful for exploring the chemistry of highly reactive cations. On the other hand, development of novel functional molecules utilizing the unique properties of C1 carborane anion (e.g., σ-aromaticity, rigid spherical skeleton) has progressed more slowly. The main reason for this is the relatively undeveloped state of synthetic chemistry in this area. Recent advances in the synthetic chemistry of C1 carborane anion are highlighted in this Concept article, focusing on cross-coupling reactions at the carbon vertex, direct conversion of B−H bonds, and the synthesis of multivalent weakly coordinating anions. These progressions move this species beyond its well-established role of highly stable “counter” monocharged anion.     

UV-induced homeotropic orientation of nematic liquid crystals dissolving two species of monomers carrying liquid-crystalline side-chain group and anthracene group

We propose the technique for formation of the polymer orientation film (POF) by polymerisation of the monomers being dissolved in the liquid crystal (LC) material for controlling the orientation of the LC molecules. For obtaining the homeotropic orientation, combination of the two monomers, 4-(4?-octyloxy-biphenyl-4-yloxy)-butyl ester (AOBBE) and 2,7-dimethacryloyl-oxy-anthracene (DMAAnth), was found to be useful. The monomer DMAAnth initiates the polymerisation under ultraviolet (UV) light exposure, and the AOBBE unit induces the homeotropic orientation. The monomer DMAAnth is useful for maintaining the high voltage holding ratio and low residual direct-current voltage after UV light exposure because the molecules of DMAAnth do not remain in the LC layer.     

On the section of a convex polyhedron

Let P be a convex polyhedron in R³, and E be a plane cutting P. Then the section P_E=P∩E is a convex polygon. We show a sharp inequality , where L(P) denotes the sum of the edge-lengths of P.     

Determination of non-stoichiometry in n-type AgBr by the measurement of transient current in an improved dc polarization cell

In order to determine the non-stoichiometry in AgBr, the transient current in a dc polarization cell, Ag/AgBr/Pt, was studied. When electrolytic current in the cell was completely blocked, only electronic current was allowed to flow through the AgBr/Pt interface, whereas both ionic and electronic carriers were transported through the Ag/AgBr interface at transient state. The ionic current through the Ag/AgBr interface was related to the change in δ in the formula of Ag_1+δBr. The following methods were proposed to determine δ from the transient current measurement: (i) The chemical diffusion coefficient, D?, of AgBr was calculated from the analysis of the time change in transient current. The electronic conductivity, σ_e, of AgBr was obtained from the steady-state current according to Wagner's theory. From D? and σ_e, δ was calculated. (ii) The transient current at the Ag/AgBr interface was divided into ionic and electronic parts using D? determined in (i). By integrating the ionic current, the change in δ was calculated. Using an improved dc polarization cell, the complete ion-blocking at the AgBr/Pt interface was achieved. The transient current after the abrupt change in applied potential was measured at 400°C. The methods (i) and (ii) were applied to the analysis of transient current and δ⁰, δ of AgBr in equilibrium with silver metal, was determined to be (2.0±0.2) x 10^-6.     

Frontiers and challenges of nuclear shell model

Two recent developments of the nuclear shell model are presented. One is a breakthrough in computational feasibility owing to the Monte Carlo Shell Model (MCSM). By the MCSM, the structure of low-lying states can be studied with realistic interactions for a wide, nearly unlimited basically, variety of nuclei. The magic numbers are the key concept of the shell model, and are shown to be different in exotic nuclei from those of stable nuclei. Its novel origin and robustness will be discussed. Received: 21 March 2002 / Accepted: 16 May 2002 / Published online: 31 October 2002 RID="a" ID="a"e-mail: otsuka@phys.s.u-tokyo.ac.jp