Synthesis of Pyrrolophenanthridine Alkaloids Based on C(sp3)H and C(sp2)H Functionalization Reactions

Assoanine, pratosine, hippadine, and dehydroanhydrolycorine belong to the pyrrolophenanthridine family of alkaloids, which are isolated from plants of the Amaryllidaceae species. Structurally, these alkaloids are characterized by a tetracyclic skeleton that contains a biaryl moiety and an indole core, and compounds belonging to this class have received considerable interest from researchers in a number of fields because of their biological properties and the challenges associated with their synthesis. Herein, a strategy for the total synthesis of these alkaloids by using C? H activation chemistry is described. The tetracyclic skeleton was constructed in a stepwise manner by C(sp³)? H functionalization followed by a Catellani reaction, including C(sp²)? H functionalization. A one‐pot reaction involving both C(sp³)? H and C(sp²)? H functionalization was also attempted. This newly developed strategy is suitable for the facile preparation of various analogues because it uses simple starting materials and does not require protecting groups.     

Extremely low vertical-emittance beam in the accelerator test facility at KEK

Electron beams with the lowest, normalized transverse emittance recorded so far were produced and confirmed in single-bunch-mode operation of the Accelerator Test Facility at KEK. We established a tuning method of the damping ring which achieves a small vertical dispersion and small x-y orbit coupling. The vertical emittance was less than 1% of the horizontal emittance. At the zero-intensity limit, the vertical normalized emittance was less than 2.8 x 10(-8) rad m at beam energy 1.3 GeV. At high intensity, strong effects of intrabeam scattering were observed, which had been expected in view of the extremely high particle density due to the small transverse emittance.     

Local chemical state change in Co–O resistance random access memory

Kelvin probe force microscopy (KFM) and conductive atomic force microscopy (C‐AFM) together with micro X‐ray photoelectron spectroscopy (XPS) were performed for the stacking structure comprising of the transition metal oxide Co–O and metal electrode, which exhibits large reproducible resistance switching. The application of the external voltage by the C‐AFM cantilever decreases the resistance of Co–O, which well accords with the non‐polar forming process observed in the Pt/Co–O/Pt trilayer, known as the candidate of resistance random access memory (ReRAM). Furthermore, the KFM and micro XPS experimentally revealed that the local reductive reaction of Co–O possibly nucleates the defect related energy levels which dominates the current conduction in the low resistance state. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Recognition and activation by ureas and thioureas: stereoselective reactions using ureas and thioureas as hydrogen-bonding donors

Hydrogen-bonding interaction plays a crucial role in the molecular recognition and activation processes of various biologically important reactions that are mediated by enzymes and antibodies in living organisms. Recently, it has been shown that a hydrogen-bonding donor can be used as a general acid catalyst for various types of reactions in organic chemistry. In this article, we describe enantioselective reactions catalyzed by urea and thiourea derivatives as general acid catalysts as well as diastereoselective reactions. This perspective provides an overview of this rapidly growing field.     

Palladium-indium iodide-mediated allylation and propargylation of glyoxylic oxime ether and hydrazone: the role of water in directing the diastereoselective allylation

Allylation and propargylation of glyoxylic oxime ether in the presence of a catalytic amount of palladium(0) complex and indium(I) iodide were studied. Excellent diastereoselectivities in allylation were achieved in the presence of water, although low diastereoselectivities were observed in the absence of water. Propargylation of glyoxylic oxime ether proceeded with good diastereoselectivities in the presence of LiBr or LiCl.     

Submillimeter-wave ESR measurements of Ca1−xCuO2 (x = 0.164) with edge-sharing CuO2 chains

Quasi-one-dimensional (1-D) cupric oxide Ca_1?xCuO₂ (x = 0.164) is the system with 25–40% hole-doped edge-sharing CuO₂ chains. However, the holes are almost localized in Ca_1?xCuO₂ and its magnetic susceptibility with a peak at 30 K was explained by the model considering both 1-D antiferromagnetic chains and spin dimers (Z. Hiroi, M. Okumura, Y. Nabeshima, T. Yamada, M. Takano: J. Phys. Soc. Jpn.69, 1824, 2000). To clarify the magnetic nature of Ca_1?xCuO₂, we performed submillimeter-wave electron spin resonance (ESR) measurements on a powder sample of Ca_0.83?6CuO₂. The resonance above 12 K showed typical powder ESR of Cu²⁺ and theg-values were determined to be g∥= 2.33 and g_⊥ = 2.06 from the analysis. The resonance below 12 K changed completely from ESR. The frequency-field relation of ESR at 1.8 K clearly showed the easy-axis type antiferromagnetic resonance.     

Polydimethylsiloxane connection for quartz microchips in a high-pressure system.

An interconnecting technique, the "PDMS connection method", for quartz microchips in a high-pressure system is presented. The connection between quartz microchips is an essential technology for modular microfluidic devices, such as microchip-HPLC. PDMS was applied to the seal material, being spread on the seal side of the chips, and set into the metal housing. The characteristics of the PDMS connection method concerning pressure resistance and the extension of the peak were examined. The experimental results showed a good seal at 5 MPa, which seem to be sufficient for realizing microchip-HPLC utilizing a monolithic silica capillary column as a separation medium. The influence of the extra column effect on chromatographic separation was almost the same as in the case using a commercial union fitting. In addition, the PDMS connection enabled the detachability of chip-based modules with user-friendliness. Our experimental findings suggest that the novel PDMS connection method can possibly be applied as a generic technology in high-pressure microTAS.     

Nonlinear viscoelastic properties and change in entanglement structure of linear polymer

Simultaneous measurements of stress relaxation and differential dynamic modulus were made at 268 K over a time scale of 10 to 10⁴⁵ s for nearly monodisperse polybutadiene (M _w =2.2x10⁵, 1,2-structure 70%, M _e =3600) and also one having coarse cross-linking (M _c =29000). Static shear strain ranged from 0.1 to 2.0. In a long-time region (t> _k ), the relaxation modulus G (; t) could be expressed by the product G (0; t) h (y). The observed h() agreed well with the Doi-Edwards theory without use of IA approximation. Both the cured and uncured samples showed initial drop of the differential storage modulus G (), ; t) followed by gradual recovery, but did not attain the value before shearing G (, ; t) for the uncured sample showed smaller values than that for the cured one in the whole measured time scale at the higher strain, confirming the two origins of nonlinear viscoelasticity of well entangled polymer; induced chain anisotropy and induced decrement in entanglement density. G (, ; t) curves for the cured sample agreed well with the BKZ predictions. But the curves for the uncured sample agreed well with the BKZ prediction only at the time scale of t< _k . BKZ prediction showed significant upward deviations at t> _k . Such the differences are discussed in terms of the two origins.Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday.     

Transient DSC,a Novel and Rapid Method for Assessing Pharmaceutical Powder Compacts

The previously described method involving the use of transient DSC was applied to pharmaceutical powder compacts and to ceramic powder compacts. The samples were prepared by compressing powders of pentaerythritol tetraacetate and two kinds of alumina powder (differing in particle size distribution) up to a pressure of 20 MPa by using a jig. For pentaerythritol tetraacetate, a linear relationship was obtained between the parameter obtained by DSC and the compaction pressure. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mössbauer and NMR studies of iron-carbon martensite

The atomic arrangements in Fe-C martensite, especially the interstitial carbon positions have been discussed utilizing⁵⁷Fe Mössbauer spectroscopy and¹³C and⁵⁷Fe spin-echo NMR measurements. The experimental result is well explained by the model of two interstices occupancy of carbon in the bct martensite. Especially, the spin-echo spectra by¹³C nuclei showed that two main lines first appear and clear satellite lines gradually rise during the aging at 323K, suggesting the carbon jumps from the tetrahedral to the octahedral interstices and further movements to form a local ordered arrangement.