Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 88 , Issue 4
Showing 1-19 articles out of 19 articles from the selected issue
Accounts for C–C Bond Formation
  • Naoya Kumagai, Masakatsu Shibasaki
    2015 Volume 88 Issue 4 Pages 503-517
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: November 17, 2014
    JOURNALS FREE ACCESS
    Recent progress (post-2010) in the field of metal-catalyzed asymmetric C–C bond-forming reactions using ketimines as electrophiles is reviewed. Compared with the corresponding aldimines, ketimines generally display less inherent reactivity and the two substituents on the imine carbon hamper prochiral-face-selection for enantioselective reactions. Recent advances with newly developed catalytic systems have resulted in several solutions to these long-standing problems. The construction of tetrasubstituted stereogenic centers is a crucial topic of asymmetric catalysis in the 21st century, and it is becoming increasingly clear that reactions using ketimines as electrophiles become one of the most important routes to access such chemical entities.
    Direct catalytic asymmetric additions to ketimines offer straightforward and efficient access to enantioenriched α-tertiary amines. Recent advances in C–C bond-forming catalysis allow for enantioselective additions of a wide variety of nucleophiles to inherently low-reactivity ketimines, which constitute an indispensable synthetic tool for the construction of tetrasubstituted stereogenic centers. Fullsize Image
     
Award Accounts
The Chemical Society of Japan Award for Creative Work for 2011
  • Kazuya Kikuchi
    2015 Volume 88 Issue 4 Pages 518-521
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: January 29, 2015
    JOURNALS FREE ACCESS
    Magnetic resonance imaging (MRI) is an imaging modality adequate for in vivo studies. Therefore, many scientists are interested in the development of MRI probes capable of detecting enzyme activities in vivo. 19F MRI is useful for monitoring particular biosignals, cells, and target tissues, due to the absence of background signals in living organisms. Therefore, highly sensitive 19F MRI contrast agents are in great demand for their practical applications. However, we have faced the following challenges: (1) increasing the number of fluorine atoms decreases the solubility of the molecular probes, and (2) the restriction of the molecular mobility attenuates the 19F MRI signals. Herein, we developed novel multifunctional core–shell nanoparticles to solve these problems. They are composed of a core micelle filled with liquid perfluorocarbon and a robust silica shell. These core–shell nanoparticles have superior properties such as high sensitivity, surface-modifiability, biocompatibility, and sufficient in vivo stability. By the adequate surface modifications, gene expression in living cells and tumor tissue in living mice were successfully detected by 19F MRI.
    A novel multifunctional core–shell nanoparticles for 19F MRI for highly sensitive detection was developed. By the adequate surface modifications, gene expression in living cells and tumor tissue in living mice were successfully detected by 19F MRI. Fullsize Image
     
BCSJ Award Article
  • Kenji Shirokane, Yuya Tanaka, Makoto Yoritate, Nobuaki Takayama, Takaa ...
    2015 Volume 88 Issue 4 Pages 522-537
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: January 20, 2015
    JOURNALS FREE ACCESS
    This article describes the full details of our total syntheses of gephyrotoxin and perhydrogephyrotoxin. Our central strategy toward the total synthesis is based on the use of an N-methoxy group as a reactivity control element. The N-methoxyamide group enabled unique transformations, involving i) the direct coupling reaction of the N-methoxyamide with an aldehyde, and ii) the amide-selective reductive allylation. These reactions were never accomplished without the assistance of the N-methoxy group. The amide-selective reductive allylation of the N-methoxyamide was especially practical, and excluded a number of extra steps including protecting group manipulations and redox reactions in the total syntheses.
    A detailed exploration of the total synthesis of (±)-gephyrotoxin and (±)-perhydrogephyrotoxin is reported. Our central strategy toward the total synthesis is based on the use of an N-methoxy group as a reactivity control element. Fullsize Image
     
 
  • Tomoaki Takayama, Akihide Iwase, Akihiko Kudo
    2015 Volume 88 Issue 4 Pages 538-543
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: January 26, 2015
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    Single-crystal KCaSrTa5O15 nanorods were successfully synthesized by a polymerized complex method. SEM and TEM observations revealed that the nanorods growing along the c axis of a tungsten bronze structure measured 40–100 nm in diameter and 100–300 nm in length. Tb(0.03 atom %)-doped KCaSrTa5O15 nanorods gave a green luminescence due to the 5D47F6 and 5D47F5 transition of Tb3+, when the KCaSrTa5O15 host was excited. The intensity of the luminescence was much higher than that by polycrystalline KCaSrTa5O15 prepared by a solid-state reaction. This indicates that nonradiative deactivation at grain boundaries was suppressed in the KCaSrTa5O15 nanorods compared to the polycrystalline KCaSrTa5O15. NiO cocatalyst-loaded KCaSrTa5O15 nanorods split water into H2 and O2 with an apparent quantum yield of 6.6% at 254 nm. The efficiency was three times as high as that of the polycrystalline KCaSrTa5O15. The KCaSrTa5O15 nanorods also showed photocatalytic activity for CO2 reduction, when a Ag-cocatalyst was loaded. Stoichiometric amounts of CO and H2 as reduction products and O2 as an oxidation product were obtained. The activity for CO2 reduction was improved by adding NaHCO3 into the reactant solution, giving about 90% CO selectivity (CO/(CO + H2)).
  • Yoshio Nakahara, Minako Higashi, Ryoto Funayama, Yasuo Horii, Hideji O ...
    2015 Volume 88 Issue 4 Pages 544-550
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: January 21, 2015
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    The stretching properties of a [7]thiaheterohelicene framework, what we call molecular spring, have not been investigated so far, despite a variety of [7]thiaheterohelicene derivatives having very interesting characteristics due to both the rigidity arising from fused benzene rings and the flexibility like a spring originating from helical structure. In this study, a novel [7]thiaheterohelicene derivative, which has a disulfide moiety for bonding to a gold-coated substrate and a carboxy group for reacting with an amino-modified probe tip at each of its end groups, was synthesized in order to elucidate the elasticity of the [7]thiaheterohelicene framework by atomic force microscopy (AFM). The AFM force measurements were carried out using two carboxy-terminated disulfide derivatives with or without a [7]thiaheterohelicene moiety, and the deviation between two kinds of force–extension curves was related to the stretching originating from the [7]thiaheterohelicene framework here. Furthermore, its elasticity was compared to that of biphenyl, which is generally known as a rigid framework, using electrostatic state calculations.
  • Shoutaro Ueno, Takeshi Kawasaki, Jun Okabayashi, Takafumi Kitazawa
    2015 Volume 88 Issue 4 Pages 551-553
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: January 19, 2015
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    We have synthesized a novel bilayered Hofmann-type 2D network complex Fe(butyl nicotinate)2[Au(CN)2]2 (I). The single crystals of I reveal a spin-crossover (SCO) transition around 200 K. Temperature-dependent X-ray absorption fine structure (XAFS) spectra indicate that I displays both SCO and aurophilic interaction properties.
  • Tatsuro Annaka, Norio Nakata, Akihiko Ishii
    2015 Volume 88 Issue 4 Pages 554-561
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: January 16, 2015
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    1,4-Bis(p-ethynylphenyl)-1-thio-1,3-butadiene derivatives incorporated in a dibenzobarrelene skeleton were yielded by Sonogashira reactions of the corresponding 1,4-bis(p-halophenyl) derivatives, and push–pull-type sulfoxide and sulfone derivatives were obtained by oxidation of the amino derivative prepared by Buchwald–Hartwig reaction of the 1,4-bis(p-halophenyl) derivatives. These compounds show red-shifted yellow and orange fluorescence [λem(CH2Cl2) = 522–562 nm, λem(solid) = 522–580 nm] in comparing with the unsubstituted, 1,4-diphenyl-1-thio-1,3-butadiene derivative [λem(CH2Cl2) = 491 nm, λem(solid) = 483 nm].
  • Toshiaki Yamashita, Motohiro Inoue, Masahide Yasuda
    2015 Volume 88 Issue 4 Pages 562-564
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: January 16, 2015
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    Photocycloaddition of 2-cyclopenten-1-one with 2,5-dihydrofuran was performed in a microreactor using the liquid–liquid slug flow consisting of water and an organic solvent to give a photochemically unstable cyclobutane, which was successfully isolated by protection using an inner filtering agent in the organic solution.
  • Keisuke Kawamoto, Akio Ichimura, Hideki Hashimoto, Isamu Kinoshita, Ma ...
    2015 Volume 88 Issue 4 Pages 565-571
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: January 16, 2015
    JOURNALS RESTRICTED ACCESS
    A novel complex with the terminal acetonitrile and bridging trifluoroacetate (tfa) ligands of [Mo3S4(dtp)3(μ-tfa)(NCCH3)] (dtp: diethyl dithiophospate) (1-tfa) was prepared from the substitution reaction of [Mo3S4(dtp)3(μ-dtp)(NCCH3)] (1-dtp) with trifluoroacetate anhydride in acetonitrile. The reaction of 1-dtp with trifluoroacetic acid in dichloromethane also afforded 1-tfa. Complex 1-tfa reacts with pyridine in ethanol resulting in the formation of a complex with the terminal pyridine ligand (py), [Mo3S4(dtp)3(μ-tfa)(py)] (2-tfa). Structures of 1-tfa and 2-tfa were determined by single-crystal X-ray structural analysis showing that one of three Mo–Mo distances depend on a kind of the bridging ligands, dtp, OAc, and tfa, while no trends in the other two Mo–Mo distances in each of the complexes with the different bridging ligands. Each of the cyclic voltammograms of 1-dtp, [Mo3S4(dtp)3(μ-OAc)(NCCH3)] (OAc: acetate) (1-OAc), 1-tfa, [Mo3S4(dtp)3(μ-OAc)(py)] (2-OAc), and 2-tfa showed two consecutive one-electron reduction waves and an oxidation wave, which are formally assigned to the Mo(IV IV IV)/Mo(III IV IV), Mo(III IV IV)/Mo(III III IV), and Mo(V IV IV)/Mo(IV IV IV) couples, respectively. The re-oxidation and re-reduction peaks for the second reduction and the oxidation processes were not observed for all of the complexes. The redox potentials of the first reduction processes were shifted up to ca. 200 mV with the bridging and terminal ligands, for example, the redox potentials appeared at −0.98 and −1.19 V vs. Fc/Fc+ 2-OAc and 1-tfa, respectively, due to the lower electron-donating ability of CH3CN and tfa ligands compared to that of the py and OAc ligands. The re-oxidation peak for the second reduction process of 2-OAc was observed at −80 °C suggesting that this is an EC process and the chemical reaction following the second electrochemical reduction is probably inhibited at low temperature. On the other hand, no re-reduction peak for the oxidation process appeared even at −80 °C implying that the oxidation process is accompanied by a significant structural change. This argument is supported by the results of the DFT calculation. The HOMO component of the complex contains a bonding character between the two acetate-bridged Mo centers and the other acetate-unbridged one, and the spin densities of the 1-electron oxidized complex mostly located at the one of two acetate-bridged Mo centers and the other acetate-unbridged one. Cyclic voltammograms of these complexes in the presence of trifluoroacetic acid as a proton source exhibited catalytic currents around the first reduction wave for each complex. The DFT calculations for 2-OAc and 2-tfa demonstrated that the HOMO components are also distributed over the doubly bridged sulfur ligands in addition to the Mo centers in the Mo3S4 core. These result suggests that a protonation reaction of 2-OAc and 2-tfa probably occurs on the doubly bridged sulfur ligand in the Mo3S4 core.
  • Takashi Kamegawa, Takahiro Ando, Yasushi Ishiguro, Hiromi Yamashita
    2015 Volume 88 Issue 4 Pages 572-574
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: January 16, 2015
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    Iron-containing mesoporous silica with hierarchical macroporous architecture (Fe-MMS) was prepared by applying a solvent evaporation method. In the hydroxylation of phenol with H2O2, the advantageous structure of Fe-MMS realized the higher selectivity for formation of dihydroxybenzene (catechol and hydroquinone) as compared to Fe-containing mesoporous silica (Fe-MS).
  • Yusuke Totsuka, Shota Ueda, Tomohisa Kuzuyama, Tetsuro Shinada
    2015 Volume 88 Issue 4 Pages 575-577
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: January 16, 2015
    JOURNALS RESTRICTED ACCESS
    Facile and stereoselective syntheses of three different kinds of deuterium-labelled geranylgeraniol analogs have been achieved. LiAlD4 is used as the deuterium source to ensure high deuterium incorporation. [8,8-d2]- and [9,9-d2]-geranylgeraniols have been prepared for the first time. [10-d]-geranylgeraniol was efficiently prepared with a high degree of deuterium incorporation.
  • Takamasa Tsukamoto, Tetsuya Shimada, Tsutomu Shiragami, Shinsuke Takag ...
    2015 Volume 88 Issue 4 Pages 578-583
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: January 19, 2015
    JOURNALS RESTRICTED ACCESS
    Photochemical chlorination and oxygenation reaction of cyclohexene sensitized by gallium(III) porphyrin–clay hybrid compound was investigated. Gallium(III) porphyrin did not aggregate on the clay surface, and thus, maintained photoactivity for the photochemical reaction. Gallium(III) porphyrin without clay decomposed immediately in the photochemical reaction. On the other hand, gallium(III) porphyrin adsorbed on clay was more stable than that without clay during the photochemical reaction and the altered porphyrin on clay still had photocatalytic ability along with original porphyrin. It was suggested that gallium(III) porphyrin was protected by clay surface during the photochemical reaction. In addition, the efficiency for the photochemical chlorination and oxygenation reaction was kept even at high porphyrin adsorption densities on clay. These findings are beneficial to construct efficient and durable photochemical reaction systems.
  • Hiromu Kumagai, Kazuhiro Takanabe, Jun Kubota, Kazunari Domen
    2015 Volume 88 Issue 4 Pages 584-590
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: January 22, 2015
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    TiN and NbN nanoparticles were synthesized from mesoporous graphitic C3N4 (mpg-C3N4) as a reactive template and used as the catalyst for ammonia synthesis. The obtained TiN and NbN nanoparticles possess high surface areas of 299 and 275 m2 g−1, respectively, making them attractive for use in catalysis and support. Although most of the TiN and NbN particles show no measurable activity for ammonia formation, the nanoparticles enabled an ammonia synthesis rate of 31 µmol h−1 g-cat−1 at 673 K and 0.1 MPa of synthesis gas (N2 + 3H2) for both TiN and NbN catalysts. It is evident that the formation of nanoparticles with high nitride surface area is essential for the materials to function as catalysts in ammonia synthesis. The addition of Fe to TiN enhanced the ammonia synthesis activity, whereas it had detrimental effects on the catalytic activity of NbN. The properties of these catalysts in ammonia synthesis are discussed.
  • Makina Saito, Francesco D’Amico, Gaia Camisasca, Filippo Bencive ...
    2015 Volume 88 Issue 4 Pages 591-596
    Published: April 15, 2015
    Released: April 15, 2015
    JOURNALS RESTRICTED ACCESS
    We report on ultraviolet resonance Raman scattering experiments carried out on two model substances: histidine and acetamide using a UV synchrotron radiation source. In the case of aqueous histidine solution each protonated state of histidine tautomers was selectively excited by tuning the incident wavelength and the vibrational state of each protonated state was studied. We also demonstrated that the local pH condition of histidine can be identified directly from the spectra above pH 9. In the case of acetamide, the resonance Raman bands of acetamide with a stronger hydrogen bond at the NH2 site and weaker hydrogen bond at the C=O site were selectively observed. These findings will extend the selectivity and sensitivity of RR spectroscopy that is helpful to understanding protein functionality.
  • I. I. Guseinov
    2015 Volume 88 Issue 4 Pages 597-599
    Published: April 15, 2015
    Released: April 15, 2015
    JOURNALS RESTRICTED ACCESS
    Using complete orthonormal L(α*)-modified self-frictional Laguerre polynomials (L(α*)-MSFLPs) in standard convention introduced by the author, the expressions for transformation of χ-noninteger Slater type orbitals (χ-NISTOs) and V-noninteger Coulomb–Yukawa-like potentials (V-NICYPs) to the MSF Laguerre power series are suggested, where α* are the integer (α* = α, −∞ < α ≤ 2) or noninteger (α* ≠ α, −∞ < α* < 3) SF quantum numbers. By the use of these power series, the atomic nuclear attraction integrals of χ-NISTOs and V-NICYPs are evaluated. The convergence and accuracy of obtained MSF Laguerre power series are tested by calculating concrete cases.
  • Tito Akindele, Baro Gise, Taiki Sunaba, Masaki Kita, Hideo Kigoshi
    2015 Volume 88 Issue 4 Pages 600-609
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: January 28, 2015
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    Stylissatin A is a proline-rich cyclic heptapeptide isolated from the Papua New Guinean marine sponge Stylissa massa. The first synthesis of stylissatin A was achieved by a combination of solid-phase and solution-phase peptide synthesis. The natural and synthetic samples of stylissatin A showed comparable inhibitory effects on nitric oxide production with negligible cytotoxicity in lipopolysaccharide (LPS)-stimulated murine macrophage RAW264.7 cells (EC50 = 73 µM for synthetic sample). Furthermore, while the D-allo-Ile5 epimer was less potent, a tert-butyl ether analog of stylissatin A was approximately six times more potent than the natural product (EC50 = 12 µM).
  • Ting Ting Yu, Lan-Jun Qi, Dong-Mei Cui, Chen Zhang, Yan Zhao
    2015 Volume 88 Issue 4 Pages 610-612
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: January 28, 2015
    JOURNALS RESTRICTED ACCESS
    N-sulfonylpyrrolidines and N-alkyl sulfonamides were efficiently prepared via alkylation of sulfonamides with 1,4-diols or alcohols by Tf2O. The reaction occurred under mild reaction conditions in moderate to high yields and tolerated aryl and aliphatic sulfonamides.
  • Kiyokazu Santo, Masakazu Hirotsu, Keisuke Kawamoto, Takanori Nishioka, ...
    2015 Volume 88 Issue 4 Pages 613-615
    Published: April 15, 2015
    Released: April 15, 2015
    [Advance publication] Released: February 10, 2015
    JOURNALS RESTRICTED ACCESS
    Ruthenium complexes containing an N,N,C,S-metalloligand or an N,N,C,O-organoligand with a sulfido carbonyl Ru cluster were obtained by the reaction of 6-(4′′-dibenzothienyl)-2,2′-bipyridine with [Ru3(CO)12]. The dibenzothienyl group undergoes double carbon–sulfur bond cleavage and CO insertion reactions to give a bridging acyl group and a metallacyclic dioxycarbene donor.
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