Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 81 , Issue 1
Showing 1-18 articles out of 18 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for 2006
  • Koichiro Oshima
    2008 Volume 81 Issue 1 Pages 1-24
    Published: January 15, 2008
    Released: January 10, 2008
    JOURNALS FREE ACCESS
    During these thirty years, we have pursued new methodologies in organic synthesis and developed many synthetically useful reactions. Among them, four topics are described in this article. (1) Regio- and stereoselective silylmetalation of acetylenes has been examined. Whereas platinum- or copper-catalyzed silylmagnesation of terminal acetylenes afforded (E)-1-silyl-1-alkene exclusively, palladium-catalyzed silylalumination with PhMe2Si-AlEt2 provided 2-silyl-1-alkenes with high regioselectivity. (2) Triethylborane induced radical addition of Ph3SnH to acetylenes gave 1-triphenylstannyl-1-alkenes in the presence of small amount of oxygen. The reaction has two distinguishing characteristics. One feature is that Et3B can initiate the radical reaction at low temperature, such as −78 °C. (3) The other distinctive feature of Et3B-induced radical reaction is that many solvents could be used for the reaction. Thus, water was chosen as a solvent, and Et3B-induced atom-transfer radical cyclization of iodo acetals and iodoacetates in water was examined. (4) Three types of organometallic ate complexes, R3MnMgBr, R3MgLi, and R3Co(L2)MgBr, were prepared and used for organic synthesis. Treatment of gem-dibromocyclopropane with trialkylmanganate provided alkylated cyclopropane after aqueous workup. Aryl and alkenyl halides could be converted into the corresponding magnesium reagents by the action of trialkylmagnesate via halogen–magnesium exchange. Finally, synthetic reactions catalyzed by cobalt complexes are described. Without suffering from β-elimination, cobalt complexes allow cross-coupling reactions of alkyl halides with Grignard reagents.
    Several new synthetic reactions have been developed: (1) Regio- and stereoselective silylmetalation of acetylenes, (2) triethylborane induced radical reactions and radical cyclization of iodoacetate in water, and (3) organic synthesis with three organometallic ate complexes (R3MnMgBr, R3MgLi, and R3Co(L2)MgBr). Fullsize Image
The Chemical Society of Japan Award for Creative Work for 2006
The Chemical Society of Japan Award for Young Chemists for 2006
  • Shigeki Matsunaga, Masakatsu Shibasaki
    2008 Volume 81 Issue 1 Pages 60-75
    Published: January 15, 2008
    Released: January 10, 2008
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    Design and applications of multimetallic bifunctional asymmetric catalysts based on the proximity-effect-control concept are described. Suitable design of chiral ligands and selection of metals were important to realize cooperative bimetallic catalysis. Homo-multimetallic complexes, using linked-BINOLs (Zn, In, Y, and La), as well as hetero-multimetallic complexes, using a dinucleating Schiff base, BINOL, and pybox (Cu–Sm, La–Li, and Y–Li), were developed for asymmetric direct aldol reactions, Michael reactions, direct Mannich-type reactions, nitro-Mannich-type reaction, aza-Michael reactions, kinetic resolution of tert-nitroaldols, and cyanation reactions. Synergistic effects of two or more metals played a key role in promoting the reactions in high reactivity and enantioselectivity.
    Design and applications of various homo- and hetero-multimetallic asymmetric catalysts based on the concept of proximity effect control are described. Strategies in designing suitable multidentate chiral ligands and selecting suitable metal combinations are introduced. Fullsize Image
BCSJ Award Article
  • Kazuyuki Ito, Takashi Matsuo, Isao Aritome, Yoshio Hisaeda, Takashi Ha ...
    2008 Volume 81 Issue 1 Pages 76-83
    Published: January 15, 2008
    Released: January 10, 2008
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    Two iron porphycene complexes having four trifluoromethyl groups, chloro-2,7,12,17-tetraethyl-3,6,13,16-tetrakis(trifluoromethyl)porphycenatoiron(III) [FeIIIClEtio(CF3)4Pc] and its μ-oxo dimer [{FeIIIEtio(CF3)4Pc}2(μ-O)], were characterized. The μ-oxo dimer was easily converted into the monomeric iron(II) complex via the Fe–O bond cleavage in pyridine. This is the first study to obtain a stable iron(II) species in a series of porphycene iron complexes. The iron(II) species crystallized in the monoclinic system C2⁄m, and the Fe–Npyridyl (2.007 Å) and Fe–Npyrrolyl (1.958 Å) bonds were remarkably short distances among the bispyridine-coordinated iron(II) porphyrins and porphyrinoids. To evaluate the influences of the CF3 substituents and framework structure on the autoreduction, we compared the reactivity of [{FeIIIEtio(CF3)4Pc}2(μ-O)] in pyridine with the reference iron porphycene and porphyrins. Autoreduction of [{FeIIIEtio(CF3)4Pc}2(μ-O)] smoothly proceeded at 20 °C in pyridine, whereas the reaction of the μ-oxo-bis{2,7,12,17-tetraethyl-3,6,13,16-tetramethylporphycenatoiron(III)} [{FeIIIEtio(CH3)4Pc}2(μ-O)] was converted into the monomeric iron(III) complex, and the iron(II) species was not available. In contrast, the μ-oxo-bis{1,3,5,7-tetrakis(trifluoromethyl)-2,4,6,8-tetraethylporphyrinatoiron(III)}[{FeIIIEtio(CF3)4Por}2(μ-O)] as a structural isomer of [{FeIIIEtio(CF3)4Pc}2(μ-O)] allowed the autoreduction, although the reaction was very slow and took over one month. These results indicate that the introduction of strong electron-withdrawing groups at the pyrrole β-carbons exhibits a unique reactivity of the iron complex.
    Trifluoromethylated iron porphycene μ-oxo dimer was easily converted into the monomeric iron(II) species via the FeIII–O–FeIII bond cleavage upon dissolution in pyridine. The reduction product was quite stable and its structure was successively determined by X-ray crystallographic analysis. Fullsize Image
 
  • Keisuke Maeda, Toshifumi Hara, Ko Furukawa, Toshikazu Nakamura
    2008 Volume 81 Issue 1 Pages 84-90
    Published: January 15, 2008
    Released: January 10, 2008
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    Multi-frequency ESR measurements using X- (9.5 GHz), Q- (34 GHz), and W-band (95 GHz) microwaves, magnetic measurement using SQUID and energy band calculation were carried out on ζ-(BEDT-TTF)2PF6(THF) and γ-(BEDT-TTF)2PF6. The temperature dependence of the spin susceptibility of the two salts shows that of typical paramagnetic insulators with low-dimensional antiferromagnetic interaction. The macroscopic magnetic behaviors are apparently similar to each other, and the absolute values of the intra-chain antiferromagnetic interaction, JintrakB, of the two salts are also close to each other. However, their ground states and microscopic behaviors indicate obvious difference. ζ-(BEDT-TTF)2PF6(THF) undergoes an antiferromagnetic transition at around 5 K, whereas γ-(BEDT-TTF)2PF6 shows no magnetic long-range ordering down to 4 K. The ESR linewidth, ΔHpp, of ζ-(BEDT-TTF)2PF6(THF) was almost temperature independent in the paramagnetic region. On the other hand, the ΔHpp of γ-(BEDT-TTF)2PF6 gradually decreased as the temperature was decreased. The low-temperature electronic states of these salts are discussed in the aspect of the magnetic dimensionality.
  • Yu Takano, Hiroshi Isobe, Kizashi Yamaguchi
    2008 Volume 81 Issue 1 Pages 91-102
    Published: January 15, 2008
    Released: January 10, 2008
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    Hemerythrin (Hr) is an oxygen-transport protein that includes a binuclear iron active site, which is found in marine invertebrates. We investigated the origin of the magnetic couplings, the nature of the chemical bond, and the mechanism of the dioxygen binding of Hr using an appropriate theoretical method and realistic models. First, we selected the appropriate functional of DFT; spin-polarized Becke’s half and half LYP (UB2LYP) showed reasonably good agreement with the experimental values. Secondly, in order to elucidate the origin of the magnetic couplings and understand the nature of the chemical bond, we estimated a range of chemical indices using natural orbitals obtained at the UB2LYP level. The results indicate that the origin of the antiferromagnetic coupling for Hr is the σ- and π-type orbital interactions via weak Fe–μO conjugation (σ- and π-type superexchange interactions) and that the difference in the strength of the dσ–pσ and dπ–pπ interactions of the diiron core in the active site of Hr is responsible for the difference in the magnetic coupling constants between oxygenated and deoxygenated Hr. Finally, using the Mulliken charge-transfer theory, we analyzed the ionization potentials of molecular oxygen and Hr. We concluded that the dioxygen binding in Hr would proceed via a two-step electron-transfer mechanism.
  • D.-M. Shafiqul Islam, Yoshiko Sasaki, Hidehito Kawauchi, Masatoshi Koz ...
    2008 Volume 81 Issue 1 Pages 103-109
    Published: January 15, 2008
    Released: January 10, 2008
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    Photoinduced electron transfer between fullerenes (C60 and C70) and three phenothiazine oligomers ((PTZ)ns; n=1, 2, and 3) was studied by using a transient absorption method in the visible and near-IR regions. Electron transfer took place from (PTZ)ns to the triplet states of fullerenes (3C60 and 3C70), giving the radical anions of fullerenes (C60•− and C70•−) and the radical cations of (PTZ)ns, which exhibited strong absorptions in visible and near-IR region for n=2 and 3. From these absorptions, positions of the radical cation in (PTZ)2•+ and (PTZ)3•+ generated by electron donation were also determined. Rate constants and quantum efficiencies of the electron transfer were found to be quite high, because of the strong electron-donating abilities of (PTZ)ns; the order of the rates of electron transfer to 3C60 and 3C70 is (PTZ)1 > (PTZ)2 = (PTZ)3, which corresponds to the decreasing order of their oxidation potentials. Upon addition of hexylviologen dication (HV2+), an electron-mediating process occurred from C60•− to HV2+, yielding the viologen radical cation (HV•+). In the presence of a sacrificial donor, HV•+ persisted for a long time.
  • Katsuhiro Tamura, Toshio Watanabe, Takayoshi Ishimoto, Umpei Nagashima
    2008 Volume 81 Issue 1 Pages 110-112
    Published: January 15, 2008
    Released: January 10, 2008
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    We performed ab initio MO-MD simulation based on the fragment MO (FMO) method using the (−)-epicatechin gallate in order to examine the efficiency of fragmentation pattern in comparison with conventional MO-MD. We clearly demonstrated that the FMO-MD simulation gave sufficient results concerning the trajectory of the total energy and the geometry difference.
  • Yoshimi Sueishi, Keitaro Miyazono, Mieko Negi, Yashige Kotake
    2008 Volume 81 Issue 1 Pages 113-115
    Published: January 15, 2008
    Released: January 10, 2008
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    We found that the addition of alkali salts significantly increased the binding between p-sulfonatocalix[8]arene and a guest group. The change in ionic strength of the solution appears to drive the functional group in the probe deep into the calixarene cavity, making it possible to detect the group-in complex by using ESR spectroscopy.
  • Rajesh Agnihotri, Nivedita Agnihotri, Jaswant Ram Mehta
    2008 Volume 81 Issue 1 Pages 116-119
    Published: January 15, 2008
    Released: January 10, 2008
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    An extractive spectrophotometric method was developed for the trace determination of tungsten in an acidic medium. A yellow-colored 1:3 complex of tungsten(VI) and 6-chloro-3-hydroxy-2-(2′-thienyl)-4-oxo-4H-1-benzopyran (CHTB), prepared in 0.16–0.32 mol dm−3 hydrochloric acid medium, was quantitatively extracted into chloroform. The complex had a maximum absorbance at 417–423 nm. The method obeyed Beer’s law in the range of 0–3.0 μg cm−3 WVI; the correlation coefficient was r=0.9902. The molar absorptivity and Sandell’s sensitivity of the complex were 4.05×104 dm3 mol−1 cm−1 and 0.0045 μg of WVI cm−2, respectively, at 420 nm. Various metals, including Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Ta, Mo, U, Zr, Th, Ce, Re, and various platinum metals did not interfere in the extraction, and this procedure was satisfactorily applied to the analysis of tungsten in various synthetic, technical and natural samples, including reverberatory flue dust and water.
  • Masahiro Narukawa, Yutaka Matsumi, Jun Matsumoto, Kenshi Takahashi, Ak ...
    2008 Volume 81 Issue 1 Pages 120-126
    Published: January 15, 2008
    Released: January 10, 2008
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    Real-time analysis of secondary organic aerosol (SOA) particles formed from 1,4-cyclohexadiene (CHD) ozonolysis in a smog chamber was performed using a laser-ionization single-particle aerosol mass spectrometer (LISPA-MS). The instrument can be used to obtain both the size and chemical compositions of individual aerosol particles with a high time-resolution (≈2 s at the maximum). Both positive- and negative-ion mass spectra can be obtained by changing the voltage polarity of the instrument. The negative-ion spectra of the SOA particles provided important information about the chemical compositions of the SOA particles. In the negative-ion spectra, intense mass peaks were determined to correspond to ions with carboxyl and aldehyde groups. The signal intensities of the intense mass peaks from compounds with carboxyl groups were higher than those from compounds with aldehyde groups as a function of the particle size. The peaks suggest that the SOA particles contain more oxygenated organic compounds as the particle size increases, namely, the chemical compositions of the SOA particles vary as a function of the particle size. We demonstrated that the real-time single-particle analysis of SOA particles by using the LISPA-MS technique can be used to clarify the formation and transformation processes of SOA particles in smog chambers.
  • Machiko Arakawa, Noriyuki Suzuki, Shinobu Kishi, Miki Hasegawa, Keiich ...
    2008 Volume 81 Issue 1 Pages 127-135
    Published: January 15, 2008
    Released: January 10, 2008
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    Mixed-ligand nickel(II) complexes Ni(acac)(dmap)X, [Ni(acac)(dmap)]BPh4 (1), [Ni(acac)(dmap)]BF4 (2), and [Ni(acac)(dmap)NO3] (3) (where acac = acetylacetonate and dmap = 1-dimethylamino-2-diphenylphosphinoethane) have been obtained for the first time and their X-ray single-crystal structures have also been determined. This series of complexes show different structures, hence colors, in the solid state depending on the coordination strength of the anion X: the complexes with tetraphenylborate and tetrafluoroborate having no coordination ability are square-planar and orange, while on the contrary, the coordinating nitrate ligand produces an octahedral and pale blue complex. In solution, two types of solvatochromism due to solute–solvent interaction and solute–solute–solvent interaction have been observed and these spectral behaviors are attributed to the changes in their geometries due to the donor/acceptor properties of the solvents. The thermochromic behavior of complex 1 has also been studied with temperature variation UV–vis spectra in various solvents. The behavior of these solvato- and thermo-chromisms of these complexes is due to the intermediate ligand field strength created by the dmap and the acac ligands.
  • Saburo Neya, Akihiro Takahashi, Hirotaka Ode, Tyuji Hoshino, Akira Ike ...
    2008 Volume 81 Issue 1 Pages 136-141
    Published: January 15, 2008
    Released: January 10, 2008
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    The iron(III) azido complex of 5,10,15,20-tetraisopropylporphyrin was characterized with NMR, EPR, Mössbauer, and magnetic susceptibility. These physical methods indicate mixing of the high (S=5⁄2) and intermediate (S=3⁄2) spin-states of the iron atom. The results were interpreted in terms of the core contraction after nonplanar deformation of porphyrin ring by the bulky isopropyl substituents. In the IR spectrum of this complex, there are two signals at 2062 and 2048 cm−1 due to the antisymmetric vibration of the coordinated azido ligand. The split IR bands demonstrate that the two spin isomers are present, and that the S=5⁄2 and 3/2 transition occurs sufficiently slow on the IR timescale. This is in remarkable contrast with the homogeneous spin-mixing model proposed for the S=5⁄2 and 3/2 system. The present observations further suggests that the three S=5⁄2, 3/2, and 1/2 states in iron(III) porphyrin commonly mix through thermal spin equilibrium.
  • Kiyoshi Honda, Hiromasa Shibuya, Hiroto Yasui, Yujiro Hoshino, Seiichi ...
    2008 Volume 81 Issue 1 Pages 142-147
    Published: January 15, 2008
    Released: January 10, 2008
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    The [2,3]sigmatropic rearrangement of allylic ammonium ylides generated by the reaction of N,N-dimethyl-1-alkyl-2-methylallylamines derived from terpene alcohols with diazo compounds in the presence of copper catalysts gave trisubstituted E-olefins in one-pot. In addition, a cyano substituent at the 2-position of N,N-dimethylallylamine increased the occurrence of the catalytic [2,3]sigmatropic rearrangement to give the corresponding bifunctional homoallylamines.
  • Setsuo Funasaka, Teruaki Mukaiyama
    2008 Volume 81 Issue 1 Pages 148-159
    Published: January 15, 2008
    Released: January 10, 2008
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    A highly useful method for the preparation of carboxylic esters and carboxamides from various carboxylic acids was established by using a novel condensing reagent, pyridine-3-carboxylic anhydride (3-PCA), in the presence of 4-(dimethylamino)pyridine as an activator. The reactions of various carboxylic acids with nucleophiles, such as alcohols or amines, afforded the corresponding carboxylic acids or carboxamides in good to high yields under mild conditions by using simple experimental procedure. In addition, it was confirmed that this protocol was applicable to a gram-scale synthesis and the by-products, including pyridine-3-carboxylic acid and pyridine-3-carboxylate (or pyridine-3-carboxamide) produced in situ, were easily removed by using a simple aqueous workup.
  • Vinod Kumar, Mahabir Parshad Kaushik
    2008 Volume 81 Issue 1 Pages 160-162
    Published: January 15, 2008
    Released: January 10, 2008
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    Reaction of aliphatic/aromatic/heterocyclic thiols with N-tert-butyl-N-chlorocyanamide in presence of sodium bromide is described. The reaction was very rapid and resulted in the formation of disulfides in excellent yields under mild conditions.
  • Sanjay Kumar Varshney, Hideo Takezoe, Doddamane Sreenivasamurthy Shank ...
    2008 Volume 81 Issue 1 Pages 163-167
    Published: January 15, 2008
    Released: January 10, 2008
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    New radial polyalkynylbenzene derivatives, which consist of 4-phenylacetylene unit connected with a central phenyl or phenoxy or tolyl linking moiety, are presented. The mesomorphic properties of these compounds in their pure form and as donor–accepter (D–A) complexes with 2,4,7-trinitrofluoren-9-one (TNF) were investigated with polarizing optical microscopy (POM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) studies. The hexaalkynylbenzene derivatives in a pure form had a columnar mesophase texture, and pentaalkynylphenyl and pentaalkynyltoluene derivatives remained in a highly viscous liquid state even at room temperature, whereas D–A complexes showed a the columnar hexagonal (Colh) mesophase. The unexpected mesophase behavior of these radial polyalkynylbenzene derivatives comes from the molecular architecture arising from the branched aliphatic chain.
  • Masaki Takahashi, Jun Kamada, Kenji Iwata, Kenichi Goto, Hiroshi Watan ...
    2008 Volume 81 Issue 1 Pages 168-170
    Published: January 15, 2008
    Released: January 10, 2008
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    Copper nanoparticles were synthesized using hydrosilanes as a reducing agent. The reaction smoothly occurred under remarkably mild conditions, i.e., room temperature. This reaction depended on the counter anions of the copper salts and the structure of the hydrosilanes, and their role is discussed.
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