Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 79 , Issue 7
Showing 1-21 articles out of 21 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Creative Work for 2004
  • Takenori Kusumi, Takashi Ooi, Yumi Ohkubo, Tetsuya Yabuuchi
    2006 Volume 79 Issue 7 Pages 965-980
    Published: 2006
    Released: July 04, 2006
    JOURNALS FREE ACCESS
    This article describes the application of the modified Mosher’s method to a variety of natural products possessing a secondary alcohol for determining their absolute configuration. The method is generally applicable to secondary alcohols with a few exceptions where the hydroxy group is seriously hindered by neighboring substituents. Countermeasures to solve the problems are also described. Recent findings that the modified Mosher’s method can be used in solvents other than deutero-chloroform are included. Development and application of the sulfoximine method for the determination of the absolute configuration of chiral sulfoxides are also described.
Accounts
  • Kiyotomi Kaneda, Kohki Ebitani, Tomoo Mizugaki, Kohsuke Mori
    2006 Volume 79 Issue 7 Pages 981-1016
    Published: 2006
    Released: July 04, 2006
    JOURNALS FREE ACCESS
    This account reviews a novel approach to designing high-performance heterogeneous metal catalysts using hydroxyapatites, montmorillonites, and hydrotalcites as macroligands of active metal species for aerobic alcohol oxidations, carbon–carbon bond formations, and one-pot syntheses. The catalytic systems using the above heterogeneous catalysts offer significant benefits in achieving environmentally friendly organic syntheses aiming towards Green and Sustainable Chemistry. Furthermore, the present preparation method for the immobilization of metal species is strikingly simple and allows a strong protocol for creating various nanostructured and functionalized heterogeneous catalysts.
BCSJ Award Article
  • Takashi Kakiuchi, Takahiro Yoshimatsu
    2006 Volume 79 Issue 7 Pages 1017-1024
    Published: 2006
    Released: July 04, 2006
    JOURNALS FREE ACCESS
    A conceptually new salt bridge based on a hydrophobic room-temperature molten salt (ionic liquid) has been demonstrated to be a promising alternative to traditional salt bridges based on a concentrated aqueous KCl phase. 1-Methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide (C8mimC1C1N), which is immiscible with water and forms a liquid–liquid two-phase system, exhibits a stable phase-boundary potential when sandwiched by two aqueous electrolyte solutions. The phase-boundary potential between the interface is determined by the partition of C8mim+ and C1C1N ions in the aqueous phase (W) and is little affected by the type of electrolytes and their concentrations in W, provided that ions dissolved in W are hydrophilic enough. The gelation of the molten salt phase does not affect the phase-boundary potential. The new salt bridge is free from most of the problems inherent to KCl-based salt bridges.
Articles
  • Koji Hasegawa, Taka-aki Ono
    2006 Volume 79 Issue 7 Pages 1025-1031
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    Normal coordinate analyses of di-μ-oxo-bridged [Mn2III,III(μ-O)2(ND3)8]2+, [Mn2III,IV(μ-O)2(ND3)8]3+, and [Mn2IV,IV(μ-O)2(ND3)8]4+ dimers were carried out systematically based on force-constants obtained by B3PW91 hybrid density functional theory (DFT) calculations on a broken-symmetry electronic state. Calculation results indicated that all Mn–O–Mn/Mn–O stretch vibrations are found at 697–387 cm−1 with the strongest infrared (IR) intensities occurring at 620, 697, and 615 cm−1 for Mn2III,III, Mn2III,IV, and Mn2IV,IV dimers, respectively, which are compatible with experimental data. These strong IR bands were assigned to the Mn–O–Mn asymmetric stretch 1 (B3u vibration) for the equivalent Mn2III,III and Mn2IV,IV dimers with D2h symmetry, and the MnIV–O symmetric stretch (A1 vibration) for the mixed-valence Mn2III,IV dimer with C2v symmetry. Based on the results of calculations, the reported 18O-sensitive IR bands in the low-frequency S2/S1 spectrum in a photosynthetic oxygen-evolving complex (OEC) were assigned to the MnIV–O asymmetric stretch (B2 vibration) in the di-μ-oxo-bridged Mn2III,IV dimer moiety for the S1-state Mn-cluster core and the Mn–O–Mn asymmetric stretch 1 (B3u vibration) in the di-μ-oxo-bridged Mn2IV,IV dimer moiety in the S2-state Mn-cluster core.
  • Yasuo Kameda, Koji Yamanaka, Motoya Sasaki, Yuko Amo, Takeshi Usuki
    2006 Volume 79 Issue 7 Pages 1032-1038
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    Neutron diffraction measurements were carried out for anion and cation exchange resins (AER and CER, respectively) absorbing H/D isotopically substituted water molecules in order to obtain structural information on the hydrogen-bonded network among water molecules within the resins. Partial structure factors, aHH(Q), aXH(Q), and aXX(Q) (X: atoms involved in the sample except for water-hydrogen atom), for AER and CER samples were respectively deduced from combined analyses of intermolecular interference terms observed for resins containing D2O (99.8% D), 0H2O (35.9% D), and 0–2H2O (67.9% D). The nearest neighbor distances, r(O···H) = 1.95(3) Å and r(H···H) = 2.40(3) Å, determined for the AER sample agree well with those reported for pure liquid water. On the other hand, considerably shorter intermolecular distances, r(O···H) = 1.78(3) Å and r(H···H) = 2.28(3) Å, were found for the CER sample, implying that the hydrogen-bonded network among water molecules in CER would be strongly affected by a highly acidic environment.
  • Sanyo Hamai
    2006 Volume 79 Issue 7 Pages 1039-1045
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    The inclusion behavior of cyclodextrins (CDs) towards neutral species of benzo[h]quinoline (BhQ), benzo[f]quinoline (BfQ), and phenanthridine (PT) have been investigated in pH 7.3 buffers. α-CD forms little or no inclusion complexes with BhQ, BfQ, and PT, whereas β-CD forms 1:1 inclusion complexes with these benzoquinolines. In β-CD solution containing propylene oxide or tetrahydrofuran, a ternary inclusion complex is formed among β-CD, the benzoquinoline, and propylene oxide (tetrahydrofuran). γ-CD forms 1:1 inclusion complexes with the benzoquinolines, except for BhQ, for which a precipitation has been observed in the concentration range examined. For BfQ, its excimer fluorescence has also been observed, which is due to the 2:2 γ-CD–BfQ inclusion complex. The equilibrium constants for the formation of the binary and ternary inclusion complexes have been evaluated from the fluorescence intensity changes.
  • Yosuke Konno, Nobuyuki Matsushita
    2006 Volume 79 Issue 7 Pages 1046-1053
    Published: 2006
    Released: July 04, 2006
    JOURNALS FREE ACCESS
    pH-Dependent color changes of an innocent diamineplatinum(II) complex, [Pt(H2L)2]Cl2 ([1]Cl2), where H2L is o-phenylenediamine, and the pH-dependent redox of non-innocent diimineplatinum(II) complexes, [Pt(L)2] (2) and [{Pt(L)2}2]Cl2 ([22]Cl2), where L is o-semibenzoquinonediimine monoanion or neutral o-benzoquinonediimine, have been investigated by vis–NIR spectroscopy and cyclic voltammetry in solutions of various pH. The crystals of [1]Cl2·2H2O and [22]Cl2·6H2O have also been characterized by X-ray crystallography. [1]Cl2 in an aqueous solution changes from colorless either to purple or to yellow-green depending on the pH of the solution. The purple solution gave a neutral complex 2 and the yellow-green solution yielded [22]Cl2·6H2O. In the latter complex, the monocation, [2]+, dimerizes forming a weak Pt–Pt bond [3.0109(4) Å] with no bridging ligands. The spectroscopy of [1]Cl2 in the buffer solutions shows that the complex 2 is formed in the range of pH 4.6–5.8, while the complex [2]+ is generated in the range of pH 2.1–4.5. These results indicate that the one-electron redox process of [2]+/2 depends on the pH of the solution. By adjusting the pH of the solution by adding acid or base, it is possible to reversibly control this redox process. This behavior is a kind of pH-dependent chromism because of their color being different.
  • M. I. Khan, Musa Kaleem Baloch, Muhammad Ashfaq, Abdul Malik
    2006 Volume 79 Issue 7 Pages 1054-1059
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    Five new diorganotin(IV) complexes of the general composition [R′2SnR2] (where R′: Me, Et, Bu, Ph, Bn and R: N-maleoyltranexamic acid) have been prepared and structurally characterized by means of FT IR and 119mSn Mössbauer spectroscopy in the solid state. The solution-state structures were determined by means of multinuclear NMR (1H, 13C, and 119Sn) spectroscopies. The spectroscopic data explained the 1:2 metal to ligand stoichiometry and hypervalency of SnIV in a trans-octahedral arrangement. Inveterate mass spectrometric and elemental analysis data has supported the solid and solution spectroscopic results. The complexes and the ligand have been evaluated in vitro against seven human tumoural cell lines. Interesting results were noticed during the bio-activity screenings, which proved their in vitro biological potential. The nature of covalent attachments (methyl, ethyl, butyl, phenyl, and benzyl) of SnIV has played a decisive role from the bioactivity stand-point.
  • Yuji Soneta, Tomoko Midorikawa, Kazuo Miyamura
    2006 Volume 79 Issue 7 Pages 1060-1062
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    (CV+)[Ni(dmit)2]·1/2(C6H6) (1) and (BF+)[Ni(dmit)2] (2) (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato, CV+ = cation of Crystal Violet, BF+ = cation of Basic Fuchsin) were prepared and characterized by X-ray crystal structural analysis. In the crystal structure of 1, the Ni(dmit)2 unit was bent at Ni in a V shape with an angle of 13.7° and tetrahedral distortion of 8.8° around Ni was also present that originated from the steric effect of the propeller-shaped CV cation. In the case of 2, BF and [Ni(dmit)2] formed an independent stacking column in which [Ni(dmit)2] were stacked alternately rotated with an angle of 90° to each other. 1 and 2 exhibited semiconducting behavior with room-temperature conductivities of 2.9 × 10−7 and 9.0 × 10−5 S cm−1, respectively.
  • Tomoharu Ama, Toshiaki Yonemura, Masayoshi Yamaguchi
    2006 Volume 79 Issue 7 Pages 1063-1065
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    Two isomers of N-(2-pyridylmethyl)glycinatocobalt(III) complexes containing incomplete cubane Co3O4 cores, [Co3(pg)33-O)(μ-OH)3]+, were isolated and their structures were determined by the X-ray diffraction method. While the trinuclear structure of one of the two isomers was stabilized by three inter-ligand N–H···O hydrogen bonds, that of the other was stabilized by two N–H···O hydrogen bonds and one inter-ligand pyridyl–pyridyl stacking interaction.
  • Nobuto Yoshinari, Yu Chikamoto, Masako Iwata, Tatsuya Kawamoto, Takumi ...
    2006 Volume 79 Issue 7 Pages 1066-1068
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    Sulfur-bridged CoIII2PtIIAgI tetranuclear complexes [Ag{Pt(NH3)2}{Co(aet)3}2](NO3)3 (1; aet = NH2CH2CH2S) and [AgPt{Co(L)}2]Cl3 (2; L = N(CH2NHCH2CH2S)3), in which two fac(S)-tris(thiolato)-type cobalt(III) units are linked by two different kinds of metal ions, PtII and AgI, were newly synthesized by the reaction of fac(S)-[Co(aet)3] with a mixture of trans-[Pt(H2O)2(NH3)2]2+ and Ag+ and by the reaction of [Ag3{Co(L)}2]3+ with [PtCl4]2−, respectively. The crystal structures of 1 and 2, which adopt racemic and meso forms, respectively, were determined by X-ray crystallography.
  • Xia Ding, Katsumi Taniguchi, Yoshihira Hamamoto, Kazunori Sada, Shuhei ...
    2006 Volume 79 Issue 7 Pages 1069-1083
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    The asymmetric 1,3-dipolar cycloaddition of nitrones possessing an electron-withdrawing group to allylic alcohols was achieved by the use of diisopropyl (R,R)-tartrate as a chiral auxiliary to afford the corresponding isoxazolidines with high regio-, diastereo-, and enantioselectivity. In the case of nitrones possessing an electron-withdrawing cyano or t-butoxycarbonyl group, 1,3-dipolar cycloaddition to 2-propen-1-ol occurred to produce the corresponding 3,5-trans-isoxazolidines with high enantioselectivity. To the contrary, nitrones possessing an amide moiety afforded the corresponding optically active 3,5-cis-isoxazolidines with completely opposite diastereoselectivity. A catalytic asymmetric 1,3-dipolar cycloaddition of nitrones possessing the N,N-diisopropylamide moiety to allylic alcohols was achieved to afford di- or trisubstituted isoxazolidines with excellent enantioselectivity of up to over 99% ee. The present asymmetric 1,3-dipolar cycloaddition was applied to the synthesis for the (2S,4R)-4-hydroxyornithine derivative.
  • Kayoko Taniguchi, Rumiko Sakurai, Kenichi Sakai, Mikio Yasutake, Takuj ...
    2006 Volume 79 Issue 7 Pages 1084-1090
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    The optical rotation properties have been studied for two diastereomeric salts of four kinds of amine–carboxylic acid salt systems, and the results have been compared among them and their chiral salts. The diastereomeric salts of 2-(4-methylphenyl)-1-phenylethylamine/mandelic acid (1-phenyl-2-(4-methylphenyl)ethylamine; PTE/MA) and α-amino-ε-caprolactam/N-tosylphenylalanine (ACL/TPA) exhibited relatively large differences in optical rotation values and solvent dependency. In contrast, the diastereomeric salts of α-methylbenzylamine/MA and piperazine-2-carboxylic acid t-butylamide/TPA possessed similar optical rotation behavior; the values and solvent dependency were almost identical. These results were discussed in relation to the dielectrically controlled resolution phenomenon for the formers, PTE/MA and ACL/TPA, and were also compared with the crystal structures.
  • Mizue Fujio, Yuzo Umezaki, Md. Ashadul Alam, Kiyoshi Kikukawa, Ryoji F ...
    2006 Volume 79 Issue 7 Pages 1091-1099
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    Solvolysis rates of 2-(dimethylphenylsilyl)-1-(Y-phenyl)ethyl 3,5-dinitrobenzoates were determined conductimetrically in 60% (v/v) aqueous ethanol. In order to clarify the nature of the β-Si participation quantitatively, the effects of α-aryl substituents on the rates were analyzed by means of the Yukawa–Tsuno Eq. The α-aryl (Y)-substituent effect at 25 °C was correlated with r 1.0 and ρ = −3.0, which is significantly reduced compared with that of −5.45 for the non-silylated 1-arylethyl system. There is a linear relationship between logkY/kH of silylated and non-silylated substrates: log(kY/kH)Si = 0.52log(kY/kH)non-Si. This is the same form as the extended Brønsted relationship. The Brønsted coefficient α = 0.52 appeared to be consistent with the neighboring silyl-participation in the silyl-bridged transition state.
  • Tadatsugu Yamaguchi, Masahiro Irie
    2006 Volume 79 Issue 7 Pages 1100-1105
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    Photochromic diarylethenes having benzofuran and benzothiophene rings have been synthesized and their photochromic performance in a single-crystalline phase has been examined. Although 1,2-bis(2-methyl-1-benzothiophen-3-yl)perfluorocyclopentene (1a) is photochemically inactive in the single-crystalline phase, diarylethene derivatives having a benzofuran ring (2a and 3a) undergo photochromism in the single-crystalline phase. 1-(1-Benzofuran-3-yl)-2-(1-benzothiophen-3-yl)hexafluorocyclopentene having ethyl, propyl, and butyl chains at the 2-position (4a6a) were also synthesized. The derivative having propyl chains (5a) underwent photochromism in a single-crystalline phase. Upon UV irradiation, the crystal showed a brilliant red color in the single-crystalline phase.
  • Kouta Masutani, Tomofumi Minowa, Yoshiaki Hagiwara, Teruaki Mukaiyama
    2006 Volume 79 Issue 7 Pages 1106-1117
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    Cyanation of various alcohols by a new type of oxidation–reduction condensation is described. Primary alkyl diphenylphosphinites, 2,6-dimethyl-1,4-benzoquinone (DMBQ), and diethyl cyanophosphonate gave the corresponding nitriles in high yields. During the above experiment on cyanation of 4-phenylbutan-2-ol, the unexpected formation of a mixture of nitrile and isocyanide was observed. After careful examination of the reaction conditions, selective synthesis of isocyanides from secondary alcohols was successfully accomplished by the use of zinc oxide (ZnO) as an additive. Reaction of tertiary alcohols provided the corresponding isocyanides exclusively in the absence of an additive. Cyanation of optically active alcohols was tried in order to clarify the stereochemistry of this reaction, and the reaction was thus proved to proceed with the inversion of configuration.
  • Mustanir, Mio Matsuoka, Masaaki Mishima, Heinz Koch
    2006 Volume 79 Issue 7 Pages 1118-1125
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    The thermodynamic stabilities of methanol-bound phenylacetylides and benzyl alkoxides were determined using a FT-ICR mass spectrometer. The complexation energies between anions and methanol were evaluated from the thermochemical cycle. The complexation energy decreases linearly with increasing acidity of the conjugate acid of an anion, giving slopes of 0.54 and 0.61 for phenylacetylide– and benzyl alkoxide–methanol complexes, respectively. These results show that the linear relationship between the complexation energy and acid–base energetics appears to be a general property in the anion–neutral molecule complexes, but the magnitude of the slope of the linear relationships is not simply related to the structure of the hydrogen-bonded complexes.
  • Kazuhiro Kobayashi, Taiyo Shiokawa, Hiroki Omote, Kenichi Hashimoto, O ...
    2006 Volume 79 Issue 7 Pages 1126-1132
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    A simple and efficient synthesis of isoquinoline and 3,4-dihydroisoquinoline derivatives is described. 1-Alkyl(or aryl)isoquinoline and 1-isoquinolinamine derivatives were obtained by intramolecular cyclization of 2-(2-methoxyethenyl)benzonitriles initiated by the addition of alkyl(or aryl)lithiums and lithium dialkylamides to the nitrile carbons, respectively. Synthesis of 4-aryl-3,4-dihydroisoquinolines was achieved by reactions of 2-(1-arylethenyl)benzonitriles with organolithiums, followed by aqueous workup. Treatment of the reaction mixtures with electrophiles prior to aqueous workup allowed the synthesis of 4,4-disubstituted 3,4-dihydroisoquinolines.
  • Yoshikazu Kawano, Nobuya Kaneko, Teruaki Mukaiyama
    2006 Volume 79 Issue 7 Pages 1133-1145
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    Lewis base-catalyzed perfluoroalkylation of carbonyl compounds and aldimines with (perfluoroalkyl)trimethylsilanes (TMSCF3, TMSC2F5, and TMSC3F7) is described. The nitrogen- or oxygen-containing anions generated from amides, imides, and carboxylic acids have been found to work as effective Lewis-base catalysts in perfluoroalkylation that proceeds via activation of the carbon–silicon bonds of (perfluoroalkyl)trimethylsilanes. Reactions of carbonyl compounds such as aldehydes, ketones, and esters with TMSCF3 in the presence of a catalytic amount of Lewis bases proceeded smoothly to afford the corresponding adducts in good-to-high yields under mild conditions. Although it was considered difficult, this catalytic perfluoroalkylation of various aldimines with (perfluoroalkyl)trimethylsilane in the presence of Lewis bases such as lithium acetate or benzoate proceeded efficiently to give the corresponding perfluoroalkylated adducts, because the aldimines here were weak electrophiles toward (perfluoroalkyl)trimethylsilanes. The present reaction is, therefore, the first example of a catalytic perfluoroalkylation of aldimines.
  • Takanori Shibata, Kazumasa Kanda, Yasunori Ueno, Ryo Fujiwara
    2006 Volume 79 Issue 7 Pages 1146-1147
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    The silylation of alcohols using allylsilanes was catalyzed by cationic Au(I) and Pt(II) species, which were prepared in situ from the metal chlorides ([AuCl(PPh3)], PtCl2) and a silver salt. TBS-, TES-, and TIPS-protections of various alcohols and carboxylic acids could be possible.
  • Yosuke Kosaka, Hiroshi M. Yamamoto, Akiko Nakao, Reizo Kato
    2006 Volume 79 Issue 7 Pages 1148-1154
    Published: 2006
    Released: July 04, 2006
    JOURNALS RESTRICTED ACCESS
    Organic conductors containing supramolecular assemblies have been obtained from the galvanostatic oxidation of donor molecules with iodine-bearing neutral molecules and halide anions. For the obtained single crystals, X-ray crystal structure analyses along with electrical and magnetic measurements were carried out. (ET)3Br(2,5-BIEP) (ET = bis(ethylenedithio)tetrathiafulvalene; 2,5-BIEP = 2,5-bis(iodoethynyl)pyridine) is isostructural with the prototype compound (ET)3Br(pBIB) (pBIB = p-bis(iodoethynyl)benzene), whereas (MT)4X(DFBIB) (MT = bis(methylenedithio)tetrathiafulvalene; DFBIB = 1,4-difluoro-2,5-bis(iodoethynyl)benzene; X = Br and Cl) and (HMTSF)4Cl3(pBIB)3(PhCl)x (HMTSF = hexamethylenetetraselenafulvalene) differ considerably from (ET)3Br(pBIB) in structure and, consequently, physical properties. The (MT)4X(DFBIB) system exhibits a novel two-dimensional donor packing, and represents the first example of the charge ordering in molecular conductors containing supramolecular assemblies based on the halogen bond. (HMTSF)4Cl3(pBIB)3(PhCl)x is characterized by isolated one-dimensional donor columns.
feedback
Top