Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 84 , Issue 7
Showing 1-16 articles out of 16 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for 2009
  • Atsuhiro Osuka, Eiji Tsurumaki, Takayuki Tanaka
    2011 Volume 84 Issue 7 Pages 679-697
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: July 02, 2011
    JOURNALS FREE ACCESS
    After a brief survey of our efforts in the development of novel porphyrinoids that include mesomeso-linked porphyrin arrays, meso-aryl expanded porphyrins, and transition-metal-catalyzed functionalizations of porphyrins, a particular focus in this account is placed on the chemistry of subporphyrins that has been explored in our group. Subporphyrin is a legitimate ring-contracted porphyrin consisting of three pyrrolic subunits domed in a C3 symmetric bowl shape. While subporphyrins are simple and small macrocycles and possess a key position in porphyrin chemistry, they had been elusive until our first synthesis of tribenzosubporphines in 2006. Shortly after, synthetic protocols of meso-aryl-substituted subporphyrins were developed to produce various subporphyrins with versatile electronic properties that can be widely tuned by meso-aryl substituents. Raney nickel reduction was used to prepare meso-alkyl-substituted subporphyrins from meso-thienyl-substituted subporphyrins. Subchlorins and subbacteriochlorins were prepared respectively by the reduction of subporphyrins with p-tosylhydrazide and Raney nickel. While subporphyrins and subchlorins share conjugated 14π-electronic circuits, subbacteriochlorins have a rare [13]diazaannulene circuit maintained through the lone-pair electrons of the nitrogen atom. The aromaticity decreases in the order of subporphyrin > subchlorin > subbacteriochlorin, as indicated from 1H- and 11B NMR spectra and nuclear independent chemical shift (NICS) calculations. Despite these progresses, the chemistry of subporphyrins is still in the infant stage with many untouched aspects and further improvements in synthetic yields are highly desirable for the developments of the chemistry of subporphyrins as well as their applications in diverse fields.
    Subporphyrins are a new class of ring-contracted porphyrinoids that were first synthesized in 2006. The chemistry of subporphyrins is reviewed with focus on the discovery, synthesis, modification, structures, supramolecular assembly, and versatile and tunable electronic properties. Fullsize Image
BCSJ Award Article
  • Satoshi Kikuchi, Shunsuke Yoshida, Yuudai Sugawara, Wataru Yamada, Hau ...
    2011 Volume 84 Issue 7 Pages 698-717
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: June 25, 2011
    JOURNALS FREE ACCESS
    A silver/DBU catalyst system was developed for the effective synthesis of cyclic carbonate and oxazolidinone from the reaction of CO2 with propargylic alcohols and propargylic amines, respectively, in high yields under mild conditions. It was found that the [3,3]-sigmatropic Meyer–Schuster-type rearrangement of the propargylic alcohol was mediated by CO2 in DMF to afford the corresponding α,β-unsaturated carbonyl compounds in high yields. The silver salt combined with the chiral Schiff base ligand could be applied to enantioselective chemical CO2 incorporation into various bispropargylic alcohols to produce the corresponding cyclic carbonate in high yields with high enantioselectivity. The absolute configuration was determined by VCD spectroscopy as well as by X-ray analysis. These products were found to be active for the aminolysis reaction to afford the corresponding carbamate derivatives in high yields without any loss of optical purity.
    In the presence of silver catalyst, cyclic carbonates, oxazolidinone, and enones were obtained in the reaction of CO2 with propargylic derivatives in good yields and optically active cyclic carbonate was also produced in good yields with high enantioselectivity. Fullsize Image
 
  • Toru Okawara, Masaaki Abe, Hisashi Shimakoshi, Yoshio Hisaeda
    2011 Volume 84 Issue 7 Pages 718-728
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: June 18, 2011
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    A series of porphycenes bearing acetoxy and hydroxy groups at the meso-positions have been prepared and fully characterized: H2TPrPc-OH, [Ni(TPrPc-OH)], H2TPrPc-OAc, and [Ni(TPrPc-OAc)], where TPrPc-OH: 9-hydroxy-2,7,12,17-tetrapropylporphycenato dianion and TPrPc-OAc: 9-acetoxy-2,7,12,17-tetrapropylporphycenato dianion. H2TPrPc-OH is structurally determined by single-crystal X-ray diffraction, showing the enol-form in the solid state. The introduction of the electron-donating hydroxy group to the meso-position decreases the HOMO–LUMO gap by ca. 0.2 eV relative to the unsubstituted parent porphycene due to the remarkable destabilization of the HOMO level. This is experimentally confirmed by red shift of the Q band in the UV–vis spectra (in CH2Cl2), negative shift of the E1/2 (in 0.1 M n-Bu4NPF6–THF), and also supported by DFT calculations. In aqueous THF, an irreversible oxidation of H2TPrPc-OH and [Ni(TPrPc-OH)] appears to be pH-dependent, with a negative Epa shift upon increasing the solution pH (in the region from 3.0 to 10.5) with slopes of −62 and −63 mV per pH unit for H2TPrPc-OH and [Ni(TPrPc-OH)], respectively, indicating the occurrence of {1H+/1e} proton-coupled electron transfer.
  • Takeharu Ishikawa, Tetsuo Iwanaga, Shinji Toyota, Mikio Yamasaki
    2011 Volume 84 Issue 7 Pages 729-740
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: June 18, 2011
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    Acyclic anthracene–acetylene trimers consisting of two 1,8-anthrylene units and one 1,5- or 1,8-anthrylene unit were cyclized by Eglinton coupling to form the corresponding cyclic trimer, hexamer, and higher oligomers. The molecular structures of these oligomers were investigated by X-ray analysis and DFT calculations at the M05/3-21G level. The trimers have rigid macrocyclic frameworks and the hexamer and higher oligomers prefer to take flat or folded structures due to transannular π···π interactions between the anthracene units. Cyclic hexamers and higher oligomers feature chiral structures that are likened to figure-eight or directional belts. The enantiomers of some chiral cyclic oligomers were resolved by chiral HPLC. The dynamic behavior of the macrocyclic frameworks and each anthrylene unit was observed by variable-temperature 1H NMR measurements. The electronic spectra of these cyclic oligomers are discussed in terms of ring size and the combination of anthrylene units.
  • Kazumi Tamura, Nor Syahidah Md Sam, Tomoyuki Ikai, Yoshio Okamoto, Eij ...
    2011 Volume 84 Issue 7 Pages 741-747
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: June 09, 2011
    JOURNALS OPEN ACCESS
    Poly(p-phenylenevinylene) (PPV) was found to be encapsulated in amylose during the polymerization of the precursor monomer in an aqueous solution. The resulting amylose–PPV composite can be further chemically modified by introducing various substituents into the hydroxy groups of the amylose using isocyanates and acetic anhydride. Here we report on the chemical modification of the amylose–PPV composite with 3,5-dimethylphenyl isocyanate in order to obtain a novel chiral packing material for resolving enantiomers by high-performance liquid chromatography (HPLC). The obtained 3,5-dimethylphenylcarbamated amylose–PPV was soluble in pyridine and exhibited a lyotropic liquid crystalline phase in a concentrated pyridine solution. The chiral recognition ability of the 3,5-dimethylphenylcarbamated amylose–PPV was different from that of amylose tris(3,5-dimethylphenylcarbamate) having no PPV rods in the helical cavity of the amylose and can resolve many racemic compounds into enantiomers. Among racemic compounds, cyclic dibenzamide and dibenzanilide derivatives were resolved on the 3,5-dimethylphenylcarbamated amylose–PPV better than amylose tris(3,5-dimethylphenylcarbamate). The difference in the enantioseparation abilities of these amylose-based chiral stationary phases for HPLC is discussed based on the difference in their helical structures.
  • Tomokazu Umeyama, Hiroyuki Fueno, Eisuke Kawabata, Yoshikazu Kobayashi ...
    2011 Volume 84 Issue 7 Pages 748-753
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: June 25, 2011
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    Theoretical investigations on single-walled carbon nanotubes (SWNTs) functionalized by Bingel reaction were conducted using finite-length models based on density functional theory. The electronic structures of the adduct with Type 1 configuration, where the circumferential C–C bonds in sidewall are reacted with a malonate anion, are largely retained after the functionalization owing to the sidewall opening at the C–C bond between the bridgehead carbons. In contrast, Type 2 configurations, where the axial C–C bonds are the reaction sites, cause significant change in the electronic structures. Taking into account the experimental results that the electronic properties of SWNTs are largely maintained, Type 1 configurations are formed selectively. In addition, calculations on energies of transition states, intermediates, and products suggest that Type 1 geometry is thermodynamically favorable but kinetically unfavorable compared to Type 2. This indicates the occurrence of isomerization from Type 2 to Type 1 after the Bingel reaction, attaining both of the preservation of electronic structure and the improvement of solubility with the high concentration of the addend group.
  • Hossein Roohi, Elham Anjomshoa
    2011 Volume 84 Issue 7 Pages 754-763
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: July 02, 2011
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    One- and two-bond spin–spin coupling constants, 1J, 1hJ, and 2hJ across X–H···Y hydrogen bonds and isotropic chemical shift of bridging hydrogens have been computed for complexes formed from interaction between the parent nitrosamine (NA) and four preferential binding sites of the uracil (U) at B3LYP/6-311++G(2d,2p)//MP2/6-311++G(2d,2p) level of theory. All complexes are stabilized by two HU···Y and HNA···Y hydrogen bonds. The correlation between spin–spin coupling constants (1hJH···Y and 2hJX···Y) and isotropic chemical shifts with the binding energy, H-bond distance, red shift of vibration frequency, charge-transfer energy, and electron density at H-bond critical point were investigated at the above-mentioned level of theory. Change in nucleus-independent chemical shift of U ring upon complex formation was also calculated.
  • Dipali Sadhukhan, Aurkie Ray, Guillaume Pilet, Georgina M. Rosair, Eug ...
    2011 Volume 84 Issue 7 Pages 764-777
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: July 02, 2011
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    Three new complexes of cobalt, manganese, and zinc have been synthesized using a hydrazone Schiff base ligand {(E)-N′-[1-(2-hydroxyphenyl)ethylidene]acetohydrazide} (LH2) produced by the 1:1 condensation of acetic hydrazide and 2-hydroxyacetophenone. The ligand has shown three different coordination modes in the three complexes: a monoanionic tridentate coordination mode with the CoII complex ([Co(LH)2]·CH3OH, 1), a dianionic tridentate coordination mode with the MnIV complex ([Mn(L)2], 2), and monoanionic μ2-phenoxo-bridged tridentate coordination mode with the ZnII complex ([Zn(LH)(OOCCF3)]2, 3). All three complexes show interesting supramolecular architectures, especially for 3 a nanoporous supramolecular (4, 4) grid 2D framework is formed. The ligand and the complexes are well characterized by elemental analysis, IR and UV–vis spectroscopy. The spin states of the CoII and MnIV metal ions and hence the coordination modes of the ligand in these complexes are in good agreement with the EPR spectroscopic data. The fluorescence emission spectra of LH2 and the zinc complex 3 are measured in acetonitrile solution as well as in solid state.
  • Mona Hosseini-Sarvari, Zahra Mardaneh
    2011 Volume 84 Issue 7 Pages 778-782
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: July 02, 2011
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    The addition reaction of acid chlorides with terminal alkynes to afford β-chloro-α,β-unsaturated ketones using ZnO as catalyst has been studied under solvent-free conditions. All the reactions were done at room temperature and β-chloro-α,β-unsaturated ketones were obtained with selectivity in high yields.
  • Shi-Yie Cheng, Shih-Tseng Lin, Shang-Kwei Wang, Chang-Yih Duh
    2011 Volume 84 Issue 7 Pages 783-787
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: June 25, 2011
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    In our screening of marine organisms for bioactive metabolites we have obtained two new α-tocopherols, designated as crassumtocopherols A (1) and B (2), from the Formosan soft coral Lobophytum crassum. The structures of 1 and 2 were determined on the basis of comprehensive NMR and HR-ESI-MS analyses. The cytotoxicity of 1, 2, natural vitamin E, and synthetic vitamin E against cancer cell lines and antiviral activity against human cytomegalovirus were evaluated in vitro. Compounds 1 and 2 exhibited moderate cytotoxicity against P-388 (mouse lymphocytic leukemia) cell lines with IC50 of 3.2 and 2.7 µg mL−1, respectively. In addition, compound 2 also displayed moderate cytotoxicity against HT-29 (human colon adenocarcinoma) with an IC50 of 3.9 µg mL−1. However, natural vitamin E and synthetic vitamin E were not cytotoxic to the selected cancer cell lines and the results for inhibition of antiviral activity against human cytomegalovirus are all negative at a concentration of 1 µg mL−1.
  • Ponnam Satyanarayana, Hariharasarma Maheswaran, Mannepalli Lakshmi Kan ...
    2011 Volume 84 Issue 7 Pages 788-790
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: July 02, 2011
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    The easy to prepare dimeric bis(μ-iodo)bis[(−)-sparteine]dicopper ([CuI{(−)-spa}]2 complex) is shown to be versatile catalyst for O-arylation and O-alkylation with various aryl halides with phenols and aliphatic alcohols respectively, including less reactive aryl chlorides, such as chlorobenzene under mild conditions.
  • Takenori Mitamura, Akiya Ogawa
    2011 Volume 84 Issue 7 Pages 791-793
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: July 02, 2011
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    Thermal aza-Bergman cyclization of o-alkynylaryl isocyanides has been achieved in the presence of organic dichalcogenides. The reactions can be induced upon heating at 40 °C to afford the corresponding 2,4-dichalcogenated quinolines. In addition, similar conditions can be also employed with iodine to form 2,4-diiodoquinolines.
  • Nagisa Minamijima, Nao Furuta, Shintaro Wakunami, Tadashi Mizutani
    2011 Volume 84 Issue 7 Pages 794-801
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: June 25, 2011
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    To construct an interface between a π-conjugated organic molecule and an inorganic/metal surface, 5,10,15,20-tetrakis[4-(5-hydroxypentyloxy)phenyl]porphyrin was chemisorbed on silica gel by refluxing in pyridine. Thermogravimetric analysis confirmed that 1.5–6.3 mg tetrahydroxyporphyrin was adsorbed on 50 mg of silica gel. To functionalize the surface of a silicate glass plate with the porphyrin, a spin-coated film of the porphyrin on the glass plate was heated at 80–296 °C, followed by sonication in pyridine to remove the unreacted porphyrin. Heating above 130 °C gave a monolayer film. The reaction proceeds between two solid phases since the melting point of the porphyrin was 293 °C. The threshold temperature for the reaction to proceed was 90, 160, and 250 °C for 5,10,15,20-tetrakis[4-(5-hydroxypentyloxy)phenyl]porphyrin, 5,10,15,20-tetrakis[4-(5-acetoxypentyloxy)phenyl]porphyrin, and 5,10,15,20-tetrakis(4-hexyloxyphenyl)porphyrin, respectively. The different reactivities of the alcohol, ester, and ether functional groups could be used to construct highly sophisticated organic–inorganic surfaces.
  • Takashi Saito, Takenori Tohyama, Patrick M. Woodward, Yuichi Shimakawa
    2011 Volume 84 Issue 7 Pages 802-806
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: July 02, 2011
    JOURNALS OPEN ACCESS
    Structural stability of A-site-ordered perovskites AMn3Al4O12 was evaluated by the global instability index calculated from the SPuDS program. Based on the results, we “designed” new compounds AMn3Al4O12 (A = Y, Yb, and Dy), and these compounds were synthesized with a high-pressure technique. The obtained compounds were ionic crystals, A3+Mn3+3Al3+4O2−12, with fourfold square-planar coordination for Mn3+ at the originally twelvefold-coordinated A site of the ABO3 simple perovskite structure. Structural parameters obtained from the structure refinement well agreed with the “predicted” values. The synthesized compounds contained magnetic Mn3+ ions with S = 2 spins at the A′ site, and the A′–A′ interaction resulted in antiferromagnetic ordering of the Mn3+ spins at temperatures ranging from 29 to 40 K. The Yb3+/Dy3+ moments in (Yb/Dy)Mn3Al4O12 were found to be paramagnetic even below the antiferromagnetic transition temperatures.
  • Soichiro Tsujimoto, Xiaojing Wang, Toshiyuki Masui, Nobuhito Imanaka
    2011 Volume 84 Issue 7 Pages 807-811
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: July 02, 2011
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    Catalytic activities for direct NO decomposition were investigated on C-type cubic Y2O3–ZrO2 and Y2O3–ZrO2–BaO prepared by coprecipitation. Introduction of excess oxide anions in the Y2O3 lattice was achieved by partial substitution of the Y3+ sites with Zr4+, and high NO decomposition activity was obtained for the (Y0.97Zr0.03)2O3.03 catalyst. In addition, the catalytic activity was further enhanced by partial substitution of the Y3+ sites in the Y2O3–ZrO2 solid solution with Ba2+, and the (Y0.89Zr0.07Ba0.04)2O3.03 catalyst exhibited the highest NO decomposition activity among the samples prepared; NO conversion to N2 reached 90% at 1173 K in the absence of O2 (NO/He atmosphere), and a relatively high conversion ratio was observed even in the presence of O2, H2O, or CO2, compared with the activities of conventional direct NO decomposition catalysts. These results indicate that the C-type cubic Y2O3–ZrO2–BaO catalyst is a new potential candidate for direct NO decomposition.
  • Norihiro Suzuki, Xiangfen Jiang, Logudurai Radhakrishnan, Kimiko Takai ...
    2011 Volume 84 Issue 7 Pages 812-817
    Published: July 15, 2011
    Released: July 15, 2011
    [Advance publication] Released: June 25, 2011
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    Here we demonstrate that photoactive titania (titanium dioxide) nanoparticles are successfully hybridized with an optimized amount of mesoporous silica (silicon dioxide) nanoparticles to realize drastic improvement of photocatalitic activity of the titania nanoparticles. Various types of mesoporous silica/titania composites are prepared by changing the amounts of doped mesoporous silica. Low-angle XRD patterns and N2 adsorption–desorption isotherms reveal that the original mesostructures and pore sizes of mesoporous silica nanoparticles are well maintained even after hybridization with the titania nanoparticles. From SEM and TEM observation, it is confirmed that both the nanoparticles are homogeneously dispersed in the composite matrix. The obtained mesoporous silica/titania composites show excellent photocatalytic activity in the decomposition of methylene blue (MB), in comparison with titania nanoparticles without mesoporous silica. By hybridization with mesoporous silica, the photogenerated radicals from titania surfaces can efficiently react with many MB molecules captured inside the mesopores.
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