Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 87 , Issue 2
Showing 1-13 articles out of 13 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for 2012
  • Shigeru Nagase
    2014 Volume 87 Issue 2 Pages 167-195
    Published: February 15, 2014
    Released: February 15, 2014
    [Advance publication] Released: November 29, 2013
    JOURNALS FREE ACCESS
    From a fundamental perspective, it is explained why the heavier main group elements provide bonds, structures, and reactions that differ from those provided by the second row elements represented by carbon, together with recent topics including transition metals. For endohedral metallofullerenes, it is explained how the cage structures, metal positions and motion, and unique properties, which are necessary for functionalization and applied investigations, are predicted and determined. The importance of close interplay between theoretical calculations and experiment is emphasized to develop new molecules and reactions using the characteristics of elements.
    It is explained why heavier main group elements provide bonds, structures, and reactions that differ from those provided by second row elements. For endohedral metallofullerenes, it is explained how the structures and unique properties are predicted and determined. Fullsize Image
     
The Chemical Society of Japan Award for Creative Work for 2012
  • Isamu Shiina
    2014 Volume 87 Issue 2 Pages 196-233
    Published: February 15, 2014
    Released: February 15, 2014
    [Advance publication] Released: October 19, 2013
    JOURNALS OPEN ACCESS
    After initially establishing a novel cyclization reaction of ω-hydroxycarboxylic acids (seco-acids) using 4-trifluoromethylbenzoic anhydride (TFBA) and Lewis acid catalysts to form the corresponding lactones, we discovered a more advanced method for this transformation using 2-methyl-6-nitrobenzoic anhydride (MNBA) as a coupling reagent with nucleophilic catalysts. The latter lactonization is promoted by acyl-transfer catalysts, such as 4-(dimethylamino)pyridine (DMAP), 4-pyrrolidinylpyridine (PPY), and 4-(dimethylamino)pyridine N-oxide (DMAPO). (+)-Ricinelaidic acid lactone ((+)-2) was first synthesized by the TFBA-mediated cyclization with Lewis acid catalysts, while the threo-aleuritic acid lactone (20) was alternatively synthesized by the MNBA-mediated cyclization with acyl-transfer catalysts. Using this effective lactonization technology to form the ester linkage under mild conditions, we then demonstrated the preparation of various large-, medium-, and small-sized natural and unnatural lactones including (−)-cephalosporolide D ((−)-3), (−)-octalactin A ((−)-4), (−)-octalactin B ((−)-25), 2-epibotcinolide (49), (−)- and (+)-2-hydroxytetracosanolides ((−)-77 and (+)-77), (−)- and (+)-2-hydroxy-24-oxooctacosanolides ((−)-78 and (+)-78), (−)-tetrahydrolipstatin ((−)-THL, (−)-117), and the erythromycin A skeletons 103b, 103c, 104c, and 105b. The transition structures involved in the formation of the β-lactones from the corresponding 3-hydroxycarboxylic acids were then determined using DFT calculations at the B3LYP/6-31G*//B3LYP/6-31G* level, and the reactivity of several seco-acids was successfully predicted on the basis of the calculated thermodynamic properties of the transition structures.
    We presented the total syntheses of cephalosporolide D, octalactins A and B, 2-epibotcinolide, 2-hydroxytetracosanolides, 2-hydroxy-24-oxooctacosanolides, and tetrahydrolipstatin, and the semisynthesis of the erythromycin A skeletons using TFBA- or MNBA-mediated effective lactonization. The reaction mechanism has been disclosed by DFT calculations. Fullsize Image
     
The Chemical Society of Japan Award for Creative Work for 2011
  • Kunio Awaga, Kenji Nomura, Hideo Kishida, Wataru Fujita, Hirofumi Yosh ...
    2014 Volume 87 Issue 2 Pages 234-249
    Published: February 15, 2014
    Released: February 15, 2014
    JOURNALS FREE ACCESS
    Heterocyclic thiazyl radicals possess unique chemical and physical properties as building blocks for molecule-based conductors and magnetic materials. They do not need protecting groups on their molecular skeletons, and the lack of such substituents permits close packing in the solid state. Moreover, thiazyl radical solids often involve a multidimensional network consisting of π–π overlaps and S···N contacts. The electronic structures of the thiazyl radicals can be compared to highly-correlated electron systems. In this account, we describe various electron-transfer processes in the solids of the thiazyl radicals, which manifest themselves by external stimuli such as temperature change, electric field, and photoillumination.
    The electronic structures of the thiazyl radical solids can be compared to highly-correlated electron systems. The present account describes various electron-transfer processes in them, which manifest themselves by external stimuli such as temperature change, electric field, and photoillumination. Fullsize Image
     
BCSJ Award Article
  • Hiroyuki Itoi, Hirotomo Nishihara, Takafumi Ishii, Khanin Nueangnoraj, ...
    2014 Volume 87 Issue 2 Pages 250-257
    Published: February 15, 2014
    Released: February 15, 2014
    [Advance publication] Released: November 22, 2013
    JOURNALS FREE ACCESS
    Zeolite-templated carbon (ZTC), which can be obtained as a negative replica of a zeolite, consists of buckybowl-like nanographenes assembled into a three-dimensional regular network. ZTC is characterized not only by this unique framework structure but also by a very large number of carbon edge sites. In this paper, we report that the edge sites of ZTC are easily functionalized by a large amount of quinone groups through electrochemical oxidation unlike general carbonaceous materials, and the quinone-functionalized ZTC shows a high electrochemical capacitance (ca. 300–500 F g−1) in an aqueous electrolyte solution (1 M H2SO4) as a result of the large pseudocapacitance derived from a quinone/hydroquinone redox couple. Moreover, ZTC keeps its high capacitance even after thousands of charge–discharge cycles.
    Zeolite-templated carbon is easily functionalized by a large amount of quinone groups through electrochemical oxidation, and the quinone-functionalized carbon shows a high electrochemical capacitance (ca. 300–500 F g−1) in an aqueous electrolyte solution. Fullsize Image
     
 
  • Lan Yao, Yukie Mori, Keiko Takano
    2014 Volume 87 Issue 2 Pages 258-266
    Published: February 15, 2014
    Released: February 15, 2014
    [Advance publication] Released: November 13, 2013
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    Inclusion complexes composed of cyclodextrin (CD) and bile acids have potential applications in drug delivery systems and chiral separation technology. In the present study, intermolecular interactions in 1:1 complexes of α-, β-, and γ-CDs with cholic acid (CA) or deoxycholic acid were analyzed both in the gas phase and in aqueous phase with density functional theory (B97-D and M06-2X) with the standard 6-31G(d) basis set together with the B3LYP functional for comparison. The association energies depend on the distance between CD and the guest as well as on the relative position and orientation of the guest in the cavity. The most stable binding mode for each complex is consistent with that proposed by NMR experiments. A pair interaction energy decomposition analysis based on ab initio fragment molecular orbital calculations was performed at the FMO-MP2/cc-pVDZ level of theory. It reveals that the β-CD/CA has more negative host–guest interaction energy than the γ-CD/CA and that dispersion and electrostatic interactions contribute comparably to the stabilization of the complexes. Several hydrogen bonds between CD and the guest also stabilize the complex.
  • Masaki Okoshi, Patchreenart Saparpakorn, Yuta Takada, Supa Hannongbua, ...
    2014 Volume 87 Issue 2 Pages 267-273
    Published: February 15, 2014
    Released: February 15, 2014
    [Advance publication] Released: November 14, 2013
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    PicoGreen (PG) is used as a probe to selectively quantitate double-stranded (ds-) DNA because it shows unique fluorescence enhancement when complexed with DNA. By binding to ds- and single-stranded (ss-) DNA, the quantum yields of PG–DNA complexes become remarkably larger than that of a free molecule. In the present theoretical study, the fluorescence enhancement mechanism of PG–DNA complexes was investigated using molecular docking simulations and ab initio quantum chemical methods. The binding energies between PG and ds-DNA were calculated to be larger than those in the case of PG and ss-DNA owing to the existence of an extra π–π stacking interaction. Nonradiative deactivation paths through conical intersections between the ground and the first excited states were obtained for a free PG molecule, while steric repulsions between PG and DNA hindered such deactivation processes in the case of PG–DNA complexes.
  • Hitomi Kamon, Yutaro Aoki, Norio Nakata, Akihiko Ishii
    2014 Volume 87 Issue 2 Pages 274-282
    Published: February 15, 2014
    Released: February 15, 2014
    [Advance publication] Released: December 05, 2013
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    A hydrido–selenolato PtII complex having P(OPh)3 ligands, cis-[PtH(SeTrip){P(OPh)3}2] (Trip: 9-triptycyl), was synthesized by the reaction of TripSeH with [Pt{P(OPh)3}2]. The structure was characterized by NMR spectroscopy and X-ray crystallography in comparison with the corresponding PPh3 complex, cis-[PtH(SeTrip)(PPh3)2], indicating the stronger coordination of P(OPh)3 to the Pt center than that of PPh3. On heating at 130 °C in xylene for 17 h, cis-[PtH(SeTrip){P(OPh)3}2] was converted to the corresponding 1,2-selenaplatinacycle (SP-4–2)-[Pt(κC1Se9-TripSe(2−)){P(OPh)3}2] through an intramolecular cyclization (cyclometalation). The reaction with dimethyl acetylenedicarboxylate (DMAD) gave a mixture of hydroselenation products (E)- and (Z)-(MeO2C)CH=C(SeTrip)CO2Me non-stereoselectively together with 1H-2-benzoselenin, dimethyl 7H-7,11b[1′,2′]-benzenoanthra[9,1-bc]selenin-2,3-dicarboxylate. In the reaction with phenylacetylene in toluene at 110 °C, phenylacetylene served as a hydrogen acceptor to form the 1,2-selenaplatinacycle and styrene. Based on the results of controlled experiments using cis-[PtD(SeTrip){P(OPh)3}2] and phenylacetylene-d, the mechanism of the cyclometalation was proposed as the 1,2- (major) and 2,1- (minor) insertions of phenylacetylene into the Pt–H bond followed by cyclometalation between the Pt center and the triptycyl group. The reaction with phenylacetylene in the presence of excess P(OPh)3 furnished a 1,2,3-oxaphosphaplatinacycle, (SP-4–2)-[Pt{κCP-(Z)-CH=C(Ph)OP(OPh)2}(SeTrip){P(OPh)3}], as a minor product, together with the 1,2-selenaplatinacycle in a decreased yield.
  • Govindaraj Venkatesh, Jayachandran Saravanan, Narayanasamy Rajendiran
    2014 Volume 87 Issue 2 Pages 283-293
    Published: February 15, 2014
    Released: February 15, 2014
    [Advance publication] Released: November 27, 2013
    JOURNALS RESTRICTED ACCESS
    The self assembly behavior of 2,4-dihydroxyazobenzene (DHAB) and 4-hydroxyazobenzene (HAB) inclusion complexes were studied by SEM and TEM. Formation of inclusion complexes were characterized by FT-IR, DSC, PXRD, 1H NMR, UV–visible, fluorescence, time-resolved fluorescence, and molecular modeling techniques. Micrometer-sized rods were observed in DHAB:α-cyclodextrin (α-CD) and DHAB:β-cyclodextrin (β-CD) inclusion complexes while microsheets were obtained in HAB/α-CD and HAB/β-CD complexes. In DHAB/CD and HAB/CD individual “barrel” type (head to head arrangement) of 2:2 inclusion complexes form microrods and microsheets through intermolecular hydrogen bonding between the neighboring complexes. Molecular modeling calculations suggest that (i) DHAB and HAB form stable complexes with α-CD and β-CD, (ii) intermolecular hydrogen bonds form between the guests and CDs. Investigations of energetic, thermodynamic, and electronic properties by PM3 method confirmed the stability of the inclusion complex.
  • Takeshi Kawasaki, Shin Okumura, Yuji Sasaki, Yasuhisa Ikeda
    2014 Volume 87 Issue 2 Pages 294-300
    Published: February 15, 2014
    Released: February 15, 2014
    [Advance publication] Released: November 25, 2013
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    Novel lanthanoid(III) (Ln(III)) complexes with N,N,N′,N′-tetraethyldiglycolamide (TEDGA), [Ln(TEDGA)3][Ln(NO3)6] (Ln = La, Ce, Pr, Nd, Sm, Eu, and Gd), have been synthesized and characterized crystallographically. The crystal structures of these complexes are constructed by the packing of [Ln(TEDGA)3]3+ cations and [Ln(NO3)6]3− anions. The [Ln(TEDGA)3]3+ cations exhibit distorted tricapped trigonal prismatic geometry, in which Ln(III) ions are coordinated by nine oxygen atoms from three tridentate TEDGA ligands. The [Ln(NO3)6]3− anions have distorted icosahedral geometry, where Ln(III) ions are coordinated by twelve oxygen atoms from the six bidentate nitrate ligands. The Ln–O bond lengths tend to increase in the following order, Ln–Onitrate > Ln–Oether > Ln–Ocarbo. Each Ln–O bond length becomes gradually short according to the lanthanoid contraction.
  • Kimihiro Komeyama, Yuya Nagao, Manabu Abe, Ken Takaki
    2014 Volume 87 Issue 2 Pages 301-313
    Published: February 15, 2014
    Released: February 15, 2014
    [Advance publication] Released: October 19, 2013
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    FeSO4-mediated direct arylation of heteroarenes with arylboronic acids in the presence of K2S2O8 has been developed. A slow addition of an aqueous solution of an iron complex was crucial in the arylation. Scope and limitation of the heteroarenes and arylboronic acids are discussed. Furthermore, the direct arylation was applied to the formal total synthesis botryllazine B and sodium channel inhibitor.
  • Ryu Tanimoto, Shuichi Suzuki, Masatoshi Kozaki, Daisuke Shiomi, Kazuno ...
    2014 Volume 87 Issue 2 Pages 314-322
    Published: February 15, 2014
    Released: February 15, 2014
    [Advance publication] Released: November 22, 2013
    JOURNALS RESTRICTED ACCESS
    We have designed and synthesized chiral molecules with nitronyl nitroxide (NN) radicals directly bound to the chiral centers, (S)-1,3-dioxolane-4-NN (1) and (R)-oxazolidine-4-NN (2). These radicals were synthesized from D-mannitol in four steps for 1 and from L-serine in six steps for 2 in moderate yields. They were characterized by means of mass spectrometry, electron spin resonance, elemental analyses, and X-ray crystal structure analyses. Their magnetic properties were also investigated using a SQUID magnetometer. The temperature dependence of paramagnetic susceptibility (χp) indicates the presence of a weak antiferromagnetic intermolecular interaction with J/kB = −3.1 K and θ = −5.5 K for 1, and a weak ferromagnetic intermolecular interaction with J/kB = +0.5 K for 2. We also succeeded in preparing the metal complex [Mn(hfac)2(2)]2–[Cu(hfac)2], which was characterized by a strong antiferromagnetic interaction (J/kB = −140 K) between [Mn(hfac)2] and 2 along with a much weaker antiferromagnetic interaction (J/kB = −0.11 K) between the [Mn(hfac)2(2)] unit and [Cu(hfac)2].
  • Ichiro Hisaki, Noriko Manabe, Keisuke Osaka, Akinori Saeki, Shu Seki, ...
    2014 Volume 87 Issue 2 Pages 323-333
    Published: February 15, 2014
    Released: February 15, 2014
    [Advance publication] Released: November 29, 2013
    JOURNALS OPEN ACCESS
    To modulate assembly manners of octadehydrodibenzo[12]annulene ([12]DBA) core in solid state, we first synthesized ortho-phenyl-substituted derivative 2 and investigated the effects of the substituents on the molecular stacking manner of the [12]DBA core. [12]DBA 2 yielded four types of crystals, which differ from that of the parent compound: Namely, the guest-free crystal possessing an offset stacking manner (I-GF), the solvate with a edge-to-face arrangement (II), the solvates with zigzag π-stacked arrangements (III and III′), and the solvate with 1D π-stacked columnar arrangements (IV). In the crystals, the phenyl groups contribute to limiting the stacking geometry of the [12]DBA cores and to forming void spaces accommodating various guest species, allowing versatile molecular assembly manners hitherto known for [12]DBA derivatives. We revealed that the crystals showed structure dependent fluorescence and charge carrier behaviors.
  • Masaki Yamamura, Masaya Iida, Kotaro Kanazawa, Masao Sasaki, Tatsuya N ...
    2014 Volume 87 Issue 2 Pages 334-340
    Published: February 15, 2014
    Released: February 15, 2014
    JOURNALS RESTRICTED ACCESS
    A trisaloph ligand L1, in which the three saloph units are macrocyclically incorporated, is a versatile multidentate ligand that maintains the multimetal complex. Structural modulation of the trisaloph complexes by anion coordination would offer more functions than the usual saloph metal complexes. In this study, the anion exchange of the heterotetranuclear complex 1(TfO)3 was applied to prepare various complexes. The two isomers, uuu- and uud-isomers, in which the coordination sites of the anions are different, were formed. The uuu-isomer was very selectively formed by using anions having a phosphate or C3-symmetric tricarboxylate.
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