Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 82 , Issue 8
Showing 1-22 articles out of 22 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for 2006
  • Keiji Maruoka
    2009 Volume 82 Issue 8 Pages 917-930
    Published: August 15, 2009
    Released: August 07, 2009
    JOURNALS FREE ACCESS
    Apart from enzymes as biocatalysts, a broad repertoire of chiral reagents, auxiliaries, and catalysts have been developed in recent years. In this respect, the design of new catalysts and new reactions in an efficient manner is increasingly important in this century for the construction of new and useful molecules. Accordingly, by designing and synthesizing sophisticated metal and non-metal catalysts, hitherto unattainable, unusual reactivity and selectivity is pursued in synthetic organic reactions. For example, the rational design of designer Lewis acids, particularly bidentate Lewis acid catalysts and their application to selective organic synthesis is carried out. In addition, the design of chiral phase transfer catalysts, chiral bifunctional organocatalysts, and chiral Brønsted acid catalysts as promising organocatalysts is realized for their application to practical asymmetric synthesis.
    This account describes that by designing sophisticated bidentate Lewis acid catalysts and organocatalysts, the hitherto unattainable, unusual reactivity and selectivity is pursued in various synthetic organic reactions. Fullsize Image
BCSJ Award Article
  • Shinji Toyota, Hiroaki Miyahara, Michio Goichi, Shingo Yamasaki, Tetsu ...
    2009 Volume 82 Issue 8 Pages 931-945
    Published: August 15, 2009
    Released: August 07, 2009
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    All the possible 1,8-anthrylene cyclic tetramers with acetylene and diacetylene linkers were synthesized as new types of π-conjugated compounds. Building units were connected by coupling reactions, and macrocyclization of the tetrameric precursors by Eglinton coupling gave the desired cyclic oligomers. Molecular structures examined by X-ray analysis and DFT calculations with the M05 functional revealed diamond prism structures with intramolecular contacts between facing anthracenes at ca. 3.5 Å. Restricted dynamic processes between the diamond forms were observed by VT 1H NMR measurements of the cyclic tetramer with one diacetylene linker and the Cs symmetric isomer with two diacetylene linkers. The enantiomers of three chiral cyclic tetramers were resolved by spontaneous resolution or chiral HPLC, and their chiroptical properties were investigated by CD spectroscopy. Absorption and emission spectra and NMR chemical shifts of these oligomers are discussed in terms of the molecular structures.
    Five title oligomers with one to four diacetylene linkers were synthesized by macrocyclization with coupling reactions. The structures and the dynamic behavior are influenced by the number and position of the diacetylene linkers. Enantiomers of chiral cyclic oligomers were resolved by chiral HPLC. Fullsize Image
 
  • Isao Kanesaka
    2009 Volume 82 Issue 8 Pages 946-952
    Published: August 15, 2009
    Released: August 07, 2009
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    The isotropic and anisotropic Raman spectra and the infrared spectrum of O–H stretching bands of CH3OH in the liquid state are analyzed on the basis of a self-consistent cluster theory based on Green’s function. The observed spectra are explained well in terms of three clusters constructed by combining two intrinsic modes. The probability of the higher and lower intrinsic modes is 0.28 and 0.72, respectively. Two intrinsic modes derived are 3425.5 and 3320.1 cm−1, where the former is recognized for the first time, and they are assigned to a H-bonded OH stretching perturbed by an OH stretching in the other chain or a Y junction and that remains unperturbed, respectively. A weak band at 3529.2 cm−1 found also for the first time is assigned to a local mode in a chain end. Overtones of the OH stretching are satisfactorily explained by fundamentals derived here. The molecules in a chain are evaluated to be 17 with mainly a tetrahedral configuration about the H-bond. In a symmetric cluster a line shape of component bands is asymmetric and their peak positions and bandwidths are discussed with a boundary parameter.
  • Seyed Hosein Mousavipour, Issa Yousefiasl
    2009 Volume 82 Issue 8 Pages 953-962
    Published: August 15, 2009
    Released: August 07, 2009
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    Quasi-classical trajectory (QCT) simulations, based on our previously reported PES data (Bull. Chem. Soc. Jpn. 2007, 80, 1901) were carried out to study the dynamics of the lowest singlet potential energy surface of H + HO2 reaction. The surface consists of two potential wells due to formation of water oxide (H2OO*) and hydrogen peroxide (HOOH*). A detailed consideration of the dynamics of the intermediates H2OO* and HOOH* reveals that water oxide and hydrogen peroxide geometries, largely undergo asymmetric or symmetric stretching like motions until they dissociate. The QCT calculations revealed that the reaction is very sensitive to the vibrational excitation of HO2. In general, QCT integral, reactive reaction cross-sections and rate constants are found to be in good agreement with their QM and experimental counterparts, indicating that, for this system, the motion of the nuclei during reactive encounters is largely classical and that quantum effects, such as tunneling, play a relatively minor role in the overall dynamics. The intramolecular vibrational energy redistribution (IVR) involving excitation of the OH and OO bonds in HOOH is investigated. The calculated IVR time constants describing energy flow out of the OH and OO stretching modes are reported. It is found that calculated IVR time constants decrease exponentially with increasing the amount of energy put in the relevant modes.
  • Shojun Hino, Takafumi Miyazaki, Yusuke Aoki, Norihiko Wanita, Masayuki ...
    2009 Volume 82 Issue 8 Pages 963-967
    Published: August 15, 2009
    Released: August 07, 2009
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    Ultraviolet photoelectron spectra (UPS) of two yttrium atoms and two carbon atoms encapsulated metallofullerenes, Y2C2@C82 were measured using a synchrotron radiation light source. Their upper valence band UPS differ significantly from each other, while the lower valence band ones are almost the same. The UPS of Y2C2@C82 (II) could be well reproduced by simulated spectra obtained with a Gaussian 03 program module assuming a distorted Y2C2 tetragonal form in C2v C82 cage structure.
  • Toru Endo, Tomoyuki Akutagawa, Teppei Kajiwara, Keiko Kakiuchi, Yoko T ...
    2009 Volume 82 Issue 8 Pages 968-974
    Published: August 15, 2009
    Released: August 07, 2009
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    Charge-transfer (CT) complexes between ethylenedithio-substituted bis-TTF macrocycle 1a, as an amphiphilic electron donor, and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) derivatives, as electron acceptors, were fabricated as Langmuir–Blodgett (LB) films. For the 1a–F4TCNQ LB film deposited at a surface pressure of 5 mN m−1 onto a substrate surface, the stoichiometry between the donor and acceptor was determined as 1:2 using XPS measurements. In contrast, a donor/acceptor ratio of 1:0.3 was observed for the 1a–Br2TCNQ LB film, indicating that a fraction of Br2TCNQ was lost during the LB film formation process. Similarity of the round-shaped domains that cover the surfaces of the 1a–Br2TCNQ and neutral 1a LB films indicates the presence of neutral 1a within the 1a–Br2TCNQ LB film. For the (1a2+)(F4TCNQ)2 LB film, the presence of a CN-stretching frequency signifies the formation of a fully ionic electronic ground state. The LB film of 1a–Br2TCNQ exhibited a broad absorption at ca. 3 × 103 cm−1, which is characteristic of an intermolecular CT transition for a partial CT state. 1a–Br2TCNQ LB film consisted of neutral 1a and CT complex of 1a–Br2TCNQ. The room temperature conductivity of the 1a–Br2TCNQ LB film (1.2 × 10−2 S cm−1) was two orders of magnitude higher than that of 1a–F4TCNQ (3.9 × 10−4 S cm−1).
  • Koji Ando
    2009 Volume 82 Issue 8 Pages 975-983
    Published: August 15, 2009
    Released: August 07, 2009
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    A semiquantal wave packet modeling of electrons in chemical bonding is presented. It is based on the valence bond (VB) theory with non-orthogonal floating and breathing spherical Gaussian orbitals, simplified to treat many electrons by decoupled electron pair approximations (DPA) and core pseudopotentials (CPP). The extended Hamiltonian formalism offers pictorial interpretation and analysis in the extended phase space of the wave packet center and width coordinates. The numerical calculations are demonstrated on the ground state potential energy surfaces of H2, LiH, and BeH2. For LiH, the perfect-pairing VB (VB-PP) calculation with the minimal orbitals gives an accurate potential energy curve of comparable quality with a correlated ab initio calculation. The two-electron VB calculation with a CPP underestimates the binding energy but gives qualitatively correct potential energy curves. For BeH2, the VB-PP with CPP gives reasonably accurate potential energy surface along both the stretching and bending coordinates. A few versions of DPA are developed and assessed, aiming toward large scale dynamic simulations. A scaling ansatz is introduced and examined on the bonding potential energy surfaces. The efficacy of the theory for studying linear and nonlinear electronic polarizations is also illustrated via an analysis of potential energy surfaces in the extended phase space.
  • Takashi Kosone, Yusuke Suzuki, Takafumi Kitazawa
    2009 Volume 82 Issue 8 Pages 984-986
    Published: August 15, 2009
    Released: August 07, 2009
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    Synthesis and crystal structures of new bimetallic polynuclear complexes in 2-dimensional (2D) architectures, [{CdII(4-OHpy)2}{NiII(CN)4}] (4-OHpy = 4-hydroxypyridine) (1) and [{CdII3(3-Opy)2(mea)2}{NiII(CN)4}2] (3-Opy = pyridin-3-onato anion, mea = monoethanolamine) (2) are described. These compounds are prepared by the same method. However, hydroxypyridine ligands are different, thus these structures differ.
  • Ping-Jyun Sung, Mei-Ru Lin, Michael Y. Chiang, Tsong-Long Hwang
    2009 Volume 82 Issue 8 Pages 987-996
    Published: August 15, 2009
    Released: August 07, 2009
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    Five new briarane derivatives, briaexcavatins V–Z (15), have been isolated from a cultured octocoral Briareum excavatum. The structures of compounds 15 were established by spectroscopic methods. Single-crystal X-ray diffraction data for 2 confirmed the structure. Briarane 4 possesses an unprecedented 8,9-epoxy moiety. The relationships between 13C NMR chemical shifts and the conformations of briaranes possessing an 11,12-epoxy group are described. Briaranes 1, 3, and 4 have displayed weak inhibitory effects on superoxide anion generation by human neutrophils. Briarane 1 was found to show mild inhibitory effects on human neutrophil elastase release and 5 exhibited mild activity to enhance human neutrophil elastase release.
  • Jin Matsumoto, Yoshiya Senda, Hiroki Masuda, Tomokazu Fuchikawa, Tsuto ...
    2009 Volume 82 Issue 8 Pages 997-999
    Published: August 15, 2009
    Released: August 07, 2009
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    4,5-Dimethoxy-2-nitrobenzyloxycarbonyl group acting as a photolabile protecting group was bonded on 3-aminopropyl silica gels through a covalent bond in a 46% yield. The deprotection was performed under UV-irradiation. The resulting amino group was analyzed through the use of a confocal laser-scanning microscope using 4-(10,15,20-triphenylporphyrinyl)phenyl fluorophore.
  • Zhen-Wu Mei, Li-Jian Ma, Hiroyuki Kawafuchi, Takumi Okihara, Tsutomu I ...
    2009 Volume 82 Issue 8 Pages 1000-1002
    Published: August 15, 2009
    Released: August 07, 2009
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    Expeditious and benign methods for primary alcohol–carboxylic acid conversions with TEMPO were developed in a biphasic system composed of a slightly miscible ether (THP) and aqueous layer. Easily available co-oxidants such as Py·HBr3, Bu4NBr3, and electrooxidation were successfully applied to generate N-oxoammonium species as a recyclable catalyst.
  • Hiroyasu Koteishi, Masaki Nojiri, Takuya Nakagami, Kazuya Yamaguchi, S ...
    2009 Volume 82 Issue 8 Pages 1003-1005
    Published: August 15, 2009
    Released: August 07, 2009
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    Cu-containing nitrite reductase from a denitrifying bacterium, Achromobacter xylosoxidans GIFU1051 (the organism formerly known as Alcaligenes xylosoxidans), can accept an electron from three possible electron donors (cytochrome c551 and two azurins). We have kinetically demonstrated that cytochrome c551 functions as a mediator in the electron flow processes between the enzyme and two azurins.
  • Ken Sakakibara, Kyoko Nozaki
    2009 Volume 82 Issue 8 Pages 1006-1008
    Published: August 15, 2009
    Released: August 07, 2009
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    Various types of sulfide–phosphine ligands and their Pd complexes were synthesized and applied to copolymerization of olefins with carbon monooxide.
  • Ken Sakakibara, Kyoko Nozaki
    2009 Volume 82 Issue 8 Pages 1009-1011
    Published: August 15, 2009
    Released: August 07, 2009
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    Two kinds of thioether–trialkylphosphine ligands and their Rh complexes were synthesized and applied to the carbonylation of methanol to acetic acid to reveal that one of the two complexes showed higher activity compared to Rh catalyst without any ligands.
  • Eiji Morita, Kei Murakami, Masayuki Iwasaki, Koji Hirano, Hideki Yorim ...
    2009 Volume 82 Issue 8 Pages 1012-1014
    Published: August 15, 2009
    Released: August 07, 2009
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    Nucleophilic substitution reactions of chlorosilanes with aryl Grignard reagents take place efficiently in the presence of copper(I) iodide to afford tetraorganosilanes.
  • Libo Fan, Tuanhui Feng, Peng Wang, Chunli Zhang, Zhibo Feng
    2009 Volume 82 Issue 8 Pages 1015-1022
    Published: August 15, 2009
    Released: August 07, 2009
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    Burr-like CuS/Cu9S5 microwires and Cu9S5 microspheres can be synthesized by a two-step solvothermal method. Experiment results indicated that the CuS/Cu9S5 microwires (diameter of ca. 300 nm and length of several micrometers) and Cu9S5 microspheres (diameter of ca. 800 nm) obtained by this method had uniform morphologies and large product. X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), and field-emission scanning electron microscopy (FE-SEM) experiments were carried out to characterize them. Fourier transform infrared (FT-IR) spectra and thermogravimetric analysis (TGA) experiments were carried out to study the components and thermal stabilization of the precursors. A possible formation mechanism and ultraviolet–visible (UV–vis) absorption spectra are also described in this paper.
  • Masaaki Haneda, Naoya Aoki, Kouji Arimitsu, Hideaki Hamada
    2009 Volume 82 Issue 8 Pages 1023-1029
    Published: August 15, 2009
    Released: August 07, 2009
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    The catalytic activity of WO3-promoted Ir/SiO2 for the selective reduction of NO with CO in the presence of excess O2 is strongly dependent on the catalyst calcination conditions in the preparation process. WO3/Ir/SiO2 catalyst prepared by air calcination showed higher activity than that prepared by H2 reduction. The activity of WO3/Ir/SiO2 catalyst prepared by air calcination was also found to increase with increasing calcination temperature up to 1073 K; however, a further increase in the temperature to 1173 K caused a decrease in the NO reduction activity, although very high selectivity was observed for this catalyst. The lack of a major difference in the apparent activation energy for NO reduction suggests that NO reduction occurs at the same reaction sites, irrespective of calcination temperature. On the other hand, the apparent activation energy for CO oxidation increased with increased calcination temperature, suggesting that the reaction sites for CO oxidation change according to calcination temperature. Catalyst characterizations revealed that iridium species interacting strongly with WO3 are preferentially created by high-temperature air calcination. A combination of partially reduced iridium species (IrO2−x) and WO3 (IrO2−x–WO3) was concluded to act as catalytically active sites of WO3/Ir/SiO2 for NO reduction.
  • Kenji Saito, Akihiko Kudo
    2009 Volume 82 Issue 8 Pages 1030-1034
    Published: August 15, 2009
    Released: August 07, 2009
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    The controlled synthesis of niobia nanowires with TT (tief–tief) phase (TT-Nb2O5-NW) that is the stable phase at low temperature was accomplished through calcination of niobium-based amorphous nanowires (Nb2O5-NW) composed of closely packed primary particles, obtained by the reaction of water-soluble niobium oxo-oxalate complex (NH4)3[NbO(Ox)3]·H2O (Ox = oxalate) with trioctylamine (TOA) employed as a structure-directing agent. TT-Nb2O5-NW gave a sharp absorption edge, which agreed well with that of the same crystalline phase of bulk niobia (TT-Nb2O5-B), suggesting no influence on the band gap energies by the shape transformation. An aqueous suspension containing TT-Nb2O5-NW and a sacrificial reagent was irradiated with white light (λ > 300 nm) from a Xe lamp to afford the enhanced photocatalytic activities for H2 or O2 evolution compared with that of conventional TT-Nb2O5-B.
  • Masataka Ohashi, Yasutomo Goto, Norihiro Mizoshita, Tetsu Ohsuna, Taka ...
    2009 Volume 82 Issue 8 Pages 1035-1038
    Published: August 15, 2009
    Released: August 07, 2009
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    Molecular orientation in 4,4′-bis(trihydroxysilyl)biphenyl plate-like square crystals (BPSi) and orientation change with heating-induced condensation were investigated using polarization optical microscopy. The biphenylylene groups in BPSi were arranged along a diagonal of the square plane with a tilt angle of 21° from the planar normal. This arrangement was maintained up to 200 °C for several minutes, but heating at 250 °C promoted a condensation reaction which formed siloxane bonds, causing changes in molecular orientation to a tilt angle of 0°, and altering the shape of BPSi crystals from square to rhombic. The molecular arrangement and its change after condensation were qualitatively confirmed by molecular-mechanics simulation. The absorption and fluorescence bands of the biphenylylene groups were significantly red-shifted by the condensation due to the change in molecular arrangement, which resulted from a notable decrease in biphenylylene–biphenylylene separation.
  • Yusuke Yamauchi, Norihiro Suzuki, Keisuke Sato, Naoki Fukata, Miwa Mur ...
    2009 Volume 82 Issue 8 Pages 1039-1043
    Published: August 15, 2009
    Released: August 07, 2009
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    Stoichiometrically controlled thiol-functionalized mesoporous silica particles are synthesized by a spray dry technique in one step. The EDS (energy dispersive X-ray spectrometer) mapping shows that thiol groups are well dispersed throughout the particles without phase separation at micrometer scale. From TEM (transmission electron microscope) observation, SAXS (small-angle X-ray scattering) measurements, and N2 adsorption–desorption isotherms, it is proven that the thiol groups can be successfully embedded in the frameworks up to 30% without any collapse of ordered mesoporous structures. The amount of the embedded thiol groups in the final products can be stoichiometrically controlled by changing the compositions of the initial precursor solutions, as is confirmed by 29Si NMR measurements. The total adsorption capacity of mercury(II) ions was increased in proportion to the amount of the thiol groups embedded in the frameworks.
  • Tomohisa Yamauchi, Yasunori Tsukahara, Tetsuo Sakamoto, Takumi Kono, M ...
    2009 Volume 82 Issue 8 Pages 1044-1051
    Published: August 15, 2009
    Released: August 07, 2009
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    We have successfully prepared face-centered cubic (fcc) Ni nanoparticles by the intramolecular reduction of Ni2+ ion contained in a formate complex having long-chain amine ligands within an extremely short time under microwave irradiation. Formate ion coordinated to Ni2+ ion acted as a reducing agent for Ni2+ in this reaction and finally decomposed to hydrogen and carbon dioxide. Ligation of the long-chain amine lowered the reaction temperatures by decreasing the energy barrier required for the reduction of the nickel formate complex. Monodisperse Ni nanoparticles with average sizes of 43, 71, and 106 nm were prepared using the complex of nickel formate with several chain lengths of alkylamines such as oleylamine (=(Z)-9-octadecenylamine), myristylamine (=tetradecylamine), and laurylamine (=dodecylamine), respectively. The relationship between the magnetic properties and the particle sizes of Ni nanoparticles is discussed.
  • Bo Liu, Song Han, Koji Tanaka, Hiroshi Shioyama, Qiang Xu
    2009 Volume 82 Issue 8 Pages 1052-1054
    Published: August 15, 2009
    Released: August 07, 2009
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    Nanocrystalline ZnO-supported platinum nanoparticles were synthesized by introducing inorganic platinum salt into the pores of MOF-5 ([Zn4O(bdc)]3; bdc = 1,4-benzenedicarboxylate) followed by heating in air at 600 °C. The Pt particle sizes can be controlled by adjusting Pt precursor concentration. The resultant Pt/ZnO samples displayed higher catalytic activity for CO oxidation than conventional Pt/ZnO catalyst.
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