Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 83 , Issue 12
Showing 1-19 articles out of 19 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Young Chemists for 2009
  • Haruhiko Fuwa
    2010 Volume 83 Issue 12 Pages 1401-1420
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: November 27, 2010
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    Total synthesis of structurally complex marine oxacyclic natural products, (−)-gambierol, (−)-brevenal, and (+)-neopeltolide, has been accomplished by exploiting Suzuki–Miyaura coupling of enol phosphates, paving the way for biological investigations on these scarcely available substances.
    Total synthesis of structurally complex marine oxacyclic natural products, (−)-gambierol, (−)-brevenal, and (+)-neopeltolide, has been accomplished by exploiting Suzuki–Miyaura coupling of enol phosphates, which paved the way for biological investigations on these scarcely available marine secondary metabolites. Fullsize Image
  • Taichi Kano, Keiji Maruoka
    2010 Volume 83 Issue 12 Pages 1421-1438
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: November 27, 2010
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    A series of chiral amines with conceptually new design have been developed as chiral organocatalysts. These chiral amine organocatalysts have been successfully applied to several asymmetric reactions via iminium and enamine intermediates and exhibited unique reactivity and selectivity in comparison with previous amine organocatalysts derived from naturally occurring amino acids. The synthetic utility of these asymmetric organocatalytic reactions has also been demonstrated in their application to the synthesis of versatile chiral building blocks.
    A series of chiral amine organocatalysts have been designed and successfully applied to several asymmetric reactions via iminium and enamine intermediates and exhibited unique reactivity and selectivity in comparison with previous chiral amine catalysts derived from natural amino acids. Fullsize Image
BCSJ Award Article
  • Keishiro Tahara, Hisashi Shimakoshi, Akihiro Tanaka, Yoshio Hisaeda
    2010 Volume 83 Issue 12 Pages 1439-1446
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: November 20, 2010
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    The electrochemical behavior of a covalently functionalized hyperbranched polymer with a vitamin B12 derivative (B12–HBP) was investigated by cyclic voltammetry and UV–vis spectroscopy combined with bulk electrolysis in N,N-dimethylformamide. The B12–HBP showed excellent properties for a homogeneous catalyst such as the good accessibilities of the cobalt centers in B12–HBP to an electrode and substrates and the maintained supernucleophilicity of the Co(I) species to alkyl halides. The cobalt-methylated B12–HBP was newly synthesized, and its electrochemical behavior was also investigated by cyclic voltammetry. Furthermore, B12–HBP was used as an electrochemical degradation catalyst for 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT). This work presents the first electrocatalysis study of a catalytically active transition-metal complex on a homogeneous dendritic support and investigates the suitability of the present B12–HBP system for electrochemical dehalogenation.
    The electrochemical behavior of a covalently functionalized hyperbranched polymer with a vitamin B12 derivative (B12–HBP) was investigated by cyclic voltammetry and UV–vis spectroscopy. The B12–HBP showed excellent properties as a homogeneous catalyst for the electrochemical degradation of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT). Fullsize Image
 
  • Tsuneki Kanzawa, Sadafumi Nishihara, Hiroyuki Nojiri, Yuko Hosokoshi
    2010 Volume 83 Issue 12 Pages 1447-1454
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: December 02, 2010
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    A new stable organic radical, 2,3,6-trifluorophenyl nitronyl nitroxide (=2-(2,3,6-trifluorophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl 3-oxide) was synthesized, and its crystal structure and magnetic properties were examined. The magnetization curve measured at 0.4 K in magnetic field up to 30 T revealed two-step saturation. A magnetization plateau was observed when the magnetization was one half the value of the saturation magnetization. The temperature dependence of the product of paramagnetic susceptibility (χp) and temperature (T), χpTpT ∝ μeff2, square of the effective magnetic moment) showed stationary behavior in the range 2–4 K at two-thirds the value at room temperature. The magnetic structure of this material could be elucidated on the basis of magnetization (M) measurements. Complementary analysis of χpT and M revealed the formation of magnetic clusters comprising triplet (S = 1) and singlet (S = 0) species in the ground state. The intradimer interactions were attributed to the special molecular overlaps, as reported previously. Interdimer interactions were also investigated: the difference in the molecular overlap between the trifluorophenyl groups was responsible for the difference in the sign of the magnetic coupling. This is the first experimental evidence for the molecular overlap between the phenyl groups being responsible for the strong magnetic interactions.
  • Jingjing Ma, Kun Qian, Weixing Huang, Yanhua Zhu, Qing Yang
    2010 Volume 83 Issue 12 Pages 1455-1461
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: November 27, 2010
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    Double-shelled CeO2 hollow microspheres (4–5 µm) were synthesized through a facile one-step hydrothermal treatment of Ce(NO3)3·6H2O in the presence of citric acid and hexamethylenetetramine (HMTA), and scanning and transmission electron microscopies demonstrated the samples are hollow spheres with litchi-like surfaces. The assembly of the hollow spheres was contributed to coordination effect of additives employed in the reaction system and the ripening growth in the process. Meanwhile, two other spherical structures including polyhedron-constituted and porous microspheres assembled with nanocrystals were also synthesized by varying the experimental parameters in the synthetic route. The UV–vis spectroscopic investigation demonstrated that the absorption edge of the three samples was blue shifted accordingly with their constituted primary crystallite sizes. In addition, investigation showed that the catalytic activities for CO oxidation of the three spheres types were considerably higher than those of commercial CeO2 powders, and their activities were in the order of porous > litchi-like double-shelled hollow > polyhedron-constituted, consistent with their BET surface area of 33, 22, and 10 m2 g−1. Specially, the litchi-like double-shelled hollow spheres showed much better catalytic properties per unit weight catalyst.
  • Gunzi Saito, Hideo Ikegami, Yukihiro Yoshida, Olga O. Drozdova, Kazuku ...
    2010 Volume 83 Issue 12 Pages 1462-1480
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: December 02, 2010
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    A series of charge-transfer (CT) solids of trifluoromethyl-7,7,8,8-tetracyanoquinodimethane (CF3TCNQ) with various electron donor molecules were prepared and their IR and UV–vis–near-IR spectra and electrical conductivity were measured. The information was applied to produce an ionicity phase diagram of CF3TCNQ CT solids. A boundary for ionicity of CF3TCNQ was found in combination with donor molecules of dibenzo[c,d]phenothiazine, diaminodurene, or dibenzotetrathiafulvalene (DBTTF). With stronger donors than DBTTF, the CF3TCNQ molecules were fully ionized and acted as a counter anion. No conductors with partially charged CF3TCNQ species were obtained. Besides the conventional 1:1 fully ionic insulators with segregated stacks, tetramethyl-TTF·CF3TCNQ·CH3CN and bis(methylthio)ethylenedithio-TTF·CF3TCNQ had fully ionic alternating stacks of DDAA units and showed Frenkel triplet excitons. (BEDO-TTF)2(CF3TCNQ) [BEDO-TTF: bis(ethylenedioxy)-TTF] consisted of a mixed-valence segregated stack of donor molecules and completely ionized acceptor molecules, and showed metallic behavior down to 1.8 K even in a compressed pellet sample. Langmuir–Blodgett films composed of (BEDO-TTF)2(CF3TCNQ) and matrix (arachidic acid) showed a conductivity of 3–6 S cm−1 at room temperature and a nearly temperature-independent conductivity down to 80 K. Semiconducting (TMTSF)2(CF3TCNQ) (TMTSF: tetramethyltetraselenafulvalene) had one-dimensional segregated stacks of dimerized TMTSF molecules separated by completely ionized CF3TCNQ, the molecular plane of which was arranged parallel to the TMTSF column. The ionicity phase diagram of the CF3TCNQ CT solids, i.e., a plot of the first CT transition energy vs. donor strength, clearly discriminated these different kinds of CT solids and will be utilized for the prediction and design of the functional CT solids.
  • Yusuke Kataoka, Yasutaka Kitagawa, Toru Saito, Yasuyuki Nakanishi, Tor ...
    2010 Volume 83 Issue 12 Pages 1481-1488
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: November 27, 2010
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    The electronic configurations and the nature of chemical bonds of the classical lantern-type dinuclear rhodium(II) tetraacetato complexes [Rh2(CH3COO)4(L)2] (L = H2O, free) have been carefully investigated with broken symmetry (BS) Hartree–Fock (HF), BS density functional theory (DFT), and BS hybrid DFT (HDFT) methods. Several electronic configurations have been proposed for the ground states of the [Rh2(RCOO)4(H2O)2] complexes. In this study, we concluded that those different electronic configurations originate from the position of the axial H2Os, and not along the Rh–Rh length. The BS(U)B3LYP calculation indicates that the stability of the σ and δ orbitals changed when the Rh–OH2 length was 2.35 Å. The natural orbital (NO) analyses and chemical indices clearly indicate that there is a σ-type single bond between the Rh ions, and that the axial H2Os does not affect the overlap.
  • Sanyo Hamai
    2010 Volume 83 Issue 12 Pages 1489-1500
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: December 02, 2010
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    In aqueous solution, inclusion complexes of several naphthalenecarboxylate derivatives with α-, β-, γ-, and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (α-CD, β-CD, γ-CD, and TM-β-CD) have been investigated by means of absorption and fluorescence spectroscopy. β-CD and TM-β-CD form 1:1 inclusion complexes with methyl 2-naphthalenecarboxylate (2NC), dimethyl 2,7-naphthalenedicarboxylate (27DNC), dimethyl 2,6-naphthalenedicarboxylate (26DNC), and dimethyl 2,3-naphthalenedicarboxylate (23DNC). α-CD forms a 2:1 α-CD–2NC inclusion complex as well as a 1:1 inclusion complex with 2NC. With 27DNC, α-CD forms a 1:1 inclusion complex alone, whereas α-CD forms a 2:1 α-CD–guest inclusion complex with 26DNC. γ-CD forms 1:1 inclusion complexes with all the naphthalenecarboxylate derivatives examined. In addition to the 1:1 inclusion complex, γ-CD forms a 2:2 γ-CD–guest inclusion complex with 27DNC (or 26DNC) through the association of the 1:1 inclusion complexes. From the 2:2 inclusion complex, the excimer fluorescence of the guest has been observed. In the case of 23DNC, γ-CD forms a 1:2 γ-CD–guest inclusion complex, from which no excimer fluorescence has been observed.
  • Hiroyuki Tominaga, Masatoshi Nagai
    2010 Volume 83 Issue 12 Pages 1501-1503
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: November 27, 2010
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    The band structures of W2C(001), WC(001), β-Mo2C(001), and Pt(111) slabs as an anode catalyst with two adsorbed hydrogen molecules using periodic DFT calculations revealed the anode performance of the carbides.
  • Keisuke Umakoshi, Kazutoyo Kimura, Yong Hun Kim, Yuya Tsukimoto, Yasuh ...
    2010 Volume 83 Issue 12 Pages 1504-1510
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: December 02, 2010
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    The pyrazolato (pz)- and 3,5-dimethylpyrazolato (Me2pz)-bridged dinuclear platinum(II) and palladium(II) complexes of 2,2′-bipyrimidine (bpym), [Pt2(bpym)2(μ-pz′)2](PF6)2 (pz′ = pz (1a) and Me2pz (1b)) and [Pd2(bpym)2(μ-pz′)2](PF6)2 (pz′ = pz (2a) and Me2pz (2b)), have been synthesized and structurally characterized. The Pd–Pt complex, [PdPt(bpym)2(μ-Me2pz)2](PF6)2 (4b), has also been synthesized and characterized by 1H NMR spectroscopy. Among these Pt2, Pd2, and PdPt complexes, only 1a and 1b exhibit greenish blue and yellow-green luminescence, respectively, in the solid state at ambient temperature. The emissions of 1a and 1b in the solid state are tentatively assigned as the emission from the 3LC/MLCT and 3MMLCT excited states, respectively.
  • Yuji Maruno, Kazuya Yabe, Hiroaki Hagiwara, Takeshi Fujinami, Naohide ...
    2010 Volume 83 Issue 12 Pages 1511-1517
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: November 27, 2010
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    Three copper(II)–gadolinium(III) complexes M[Gd(CuL)4] with M+ = Na+, K+, and Cs+ have been synthesized, where H3L denotes N-(4-methyl-6-oxo-3-azahept-4-enyl)oxamic acid. The anionic part [Gd(CuL)4] assumes a pinwheel-like pentanuclear GdCu4 core and the central GdIII ion is coordinated by eight oxygen atoms of four “(CuL),” where each “(CuL)” assumes a square-planar N2O2 coordination geometry and functions as a bidentate chelate ligand to GdIII ion. The sodium and potassium salts assume a one-dimensional (1D) chain structure bridged by Na+ or K+ ions, while the cesium salt assumes a cyclic dimeric structure bridged by Cs+ ions. For the assembly structures, the cation acts as a connector between adjacent [Ln(CuL)4] cores. The magnetic data demonstrated an intracluster ferromagnetic interaction between GdIII and CuII ions within a GdCu4 core and an intercluster antiferromagnetic interaction through the cation. The magnetic susceptibilities can be reproduced by the spin Hamiltonian based on the pentanuclear GdCu4 structure, &bcsj_2010_20100023; = βH(4gCuSCu + gGdSGd) − 2JSGd(SCu1 + SCu2 + SCu3 + SCu4). The best-fit parameters are gGd = 2.00, gCu = 2.12, JGd–Cu = +1.11 cm−1, zJ′ = −0.065 cm−1, and 0.4% of monomeric CuII impurity for the Na+ salt,; gGd = 2.00, gCu = 2.13, JGd–Cu = +1.03 cm−1, zJ′ = −0.038 cm−1, and 0.2% of monomeric CuII impurity for the K+ salt,; and gGd = 2.00, gCu = 2.14, JGd–Cu = +0.67 cm−1, zJ′ = −0.025 cm−1, 0.2% of monomeric CuII impurity for the Cs+ salt. The Gd–Cu coupling constant J is very similar in the Na+ and K+ salts (+1.11 and +1.03 cm−1) but is slightly smaller for the Cs+ salt (+0.67 cm−1), probably due to the different packing of the GdCu4 clusters in the latter salt (cyclic dimers instead of an infinite chain); (2) the intercluster antiferromagnetic interaction, responsible for the low temperature decrease of χMT, significantly decreases when the ionic radius of the alkali cation increases (Na+ < K+ < Cs+) thus keeping the pentanuclear units further apart.
  • Mari Toyama, Shinobu Iwamatsu, Ken-ichi Inoue, Noriharu Nagao
    2010 Volume 83 Issue 12 Pages 1518-1527
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: December 02, 2010
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    The labile cationic aqua complexes, trans(O,S)-[Ru(bpy)Cl(dmso-S)2(OH2)]X (1·X; X = PF6 or OTf: CF3SO3) have been prepared by the treatment of cis(Cl),cis(S)-[Ru(bpy)Cl2(dmso-S)2] with Ag+ in water at room temperature. When 1·X is dissolved in DMSO, MeOH, or MeCN, the OH2 ligand in 1+ is replaced with a solvent molecule (L) to yield trans(L,S)-[Ru(bpy)Cl(dmso-S)2(L)]+ (L = dmso-O, 2+; L = MeOH, 3+; and L = MeCN, 4+), respectively. Moreover, 2·(OTf) is also obtained by the reaction of cis(Cl),cis(S)-[Ru(bpy)Cl2(dmso-S)2] with Ag(OTf) in DMSO on refluxing. The four kinds of crystal structures of trans(L,S)-[Ru(bpy)Cl(dmso-S)2(L)]PF6 (1·PF6·H2O, 2·PF6, 3·PF6, and 4·PF6·MeCN) revealed that the structural parameters, except for the sixth axial ligand, were essentially the same, and the four ligands, the bpy, two dmso-S, and the equatorial Cl ligands are connected by hydrogen bonding. All the OH2, dmso-O, MeOH, or MeCN ligands on the sixth coordination site at the axial position in cationic mono(bpy)ruthenium(II) complexes are labile so they are interconvertable. The [Ru(bpy)Cl(dmso-S)2] unit does not change at room temperature even in solutions due to the presence of hydrogen networks among the bpy, two dmso-S, and the equatorial Cl ligands.
  • Takeshi Kawasaki, Tatsuru Nishimura, Takafumi Kitazawa
    2010 Volume 83 Issue 12 Pages 1528-1530
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: December 02, 2010
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    Seven uranyl(VI) complexes, [UO2(acac)2(L)] [L = 4-methylpyridine (1), 4-ethylpyridine (2), 2,4-dimethylpyridine (3), (−)-nicotine (4), and imidazole (5)], [{UO2(acac)2}2(4,4′-bipyridine)] (6), and [(2,2′-bipyridine)2H][UO2(acac)(NO3)2] (7) have been synthesized and characterized crystallographically. The coordination geometry of U has a UNO6 pentagonal-bipyramidal coordination in 16, and a UO8 hexagonal-bipyramidal coordination in 7.
  • Menchie E. Montecillo, Toshifumi Yoshidome, Toshiyuki Yamagata, Tatsuy ...
    2010 Volume 83 Issue 12 Pages 1531-1533
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: December 02, 2010
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    A surface plasmon resonance (SPR) sensor with agar membrane was developed and applied to aqueous solutions containing methanol and raffinose. The concentrations of the components in the mixture were determined by fitting diffusion-based equations to the SPR time chart. Good agreement between the measured and expected concentrations was observed.
  • Atsushi Torihata, Chiaki Kuroda
    2010 Volume 83 Issue 12 Pages 1534-1538
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: November 27, 2010
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    The extent of hydrophobic effect in amidation reaction of alkyl thioester with alkylamine in water was studied. The yield of the products was primarily dependent on the alkyl group of amine. For example, the reaction of S-dodecyl dodecanethioate with dodecylamine proceeded in good yield, while the reaction did not occur with cyclohexylamine, piperidine, and dipropylamine. The effect of chain length of n-alkylamine was studied to suggest the presence of hydrophobic effect. The yield of amide also depended on the alkyl group of the thioester secondarily, but the effect was smaller than amine.
  • Masa-aki Sato, Hirokazu Kamine, Takumi Kato
    2010 Volume 83 Issue 12 Pages 1539-1544
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: November 27, 2010
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    Unsymmetrically substituted quaterthiophenes with two terminal ferrocenyl groups were prepared as long π-conjugated systems. Anisotropy of the chemical structures of the π-conjugated systems was introduced by substitution of methoxy and hexyl groups. Electrochemical and spectroscopic studies were carried out to evaluate the oxidation states of the diferrocenylquaterthiophenes and the interaction between the two terminals. The one-electron oxidation of one diferrocenylquaterthiophene adequately substituted with two methoxy and one hexyl group occurs at one ferrocene moiety specified due to the unsymmetry of the quaterthiophene moiety. The one-electron oxidizing species extends into the quaterthiophene moiety and apparently interacts with the other terminal ferrocene moiety.
  • Li-Jian Ma, Zhen-Wu Mei, Keisuke Toyohara, Hiroyuki Kawafuchi, Junzo N ...
    2010 Volume 83 Issue 12 Pages 1545-1547
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: December 02, 2010
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    O-(2-Alkenoyl)TEMPOs bearing an O–N bond in the acyl substituent are highly reactive in Michael addition of magnesium amide compared with their acyl substituent-modified analogs. Highly diastereoselective addition is achieved to the AlMe3-treated O-(2-alkenoyl)TEMPO as an acceptor with the Mg amide generated from optically active secondary amine.
  • Hitoshi Tamiaki, Hidetada Morishita
    2010 Volume 83 Issue 12 Pages 1548-1550
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: November 20, 2010
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    Zinc and cadmium complexes of methyl 31-demethylbacteriopheophorbide-d 18O-labeled specifically at the 131-oxo moiety were prepared. The FT-IR vibrational band of the 13-carbonyl group was shifted to a much lower wavenumber by their self-aggregation, similarly as in natural light-harvesting antennae.
  • Jin Matsumoto, Koshiro Yoneda, Jun Tasaka, Tsutomu Shiragami, Masahide ...
    2010 Volume 83 Issue 12 Pages 1551-1557
    Published: December 15, 2010
    Released: December 15, 2010
    [Advance publication] Released: December 02, 2010
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    A mixture of sodium 1,2-di(hexadecyloxycarbonyl)ethanesulfonate (2C16S) with photopolymerizable 1,2-di(10,12-tricosadiynoyl)-sn-glycerol 3-phosphocholine (DTPC) in a 2:100 ratio was treated by modified thin-film hydration to give an aggregate which became polymerized giant vesicles (GVs) under irradiation at 254 nm. The autofluorescence of the GVs was analyzed with a confocal laser scanning microscope at the cross section, revealing a 3.8-µm diameter ring shape and the presence of a dark part of ca. 1 µm in the ring. When octadecylrhodamine B (RhB) as an amphiphilic fluorescence probe was added to the GV, the fluorescence of RhB was emitted from the whole ring. Therefore, phase segregation of 2C16S from DTPC was confirmed. Similarly, mixed vesicles of N,N-di(2-hexadecanoyloxyethyl)dimethylammonium iodide with DTPC were found to be 3.7-µm diameter phase-segregated vesicles with a dark portion of ca. 1 µm on the ring in the cross sectional image. On the other hand, DTPC vesicles mixed with 1,2-di(dodecyloxycarbonyl)ethanesulfonate, N,N-di(2-dodecanoyloxyethyl)dimethylammonium iodide, and N,N-di(2-tetradecanoyloxyethyl)dimethylammonium iodide formed sphere structures filling the inside of the vesicles. The segregation mechanism was explained by the difference in the main phase transition temperature of each amphiphile.
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