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軸不斉と有機触媒で修飾されたナノ細孔の構築と不斉認識・不斉反応

Research Project

Project/Area Number 18033052
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionKanagawa University

Principal Investigator

森 和亮  Kanagawa University, 理学部, 教授 (60029709)

Co-Investigator(Kenkyū-buntansha) 木原 伸浩  神奈川大学, 教授 (30214852)
Project Period (FY) 2006 – 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 2007: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 2006: ¥1,900,000 (Direct Cost: ¥1,900,000)
Keywords結晶工学 / 自己組織化 / 超格子 / 分子認識 / 不斉反応
Research Abstract

(+)-樟脳酸の銅塩のピラジン、ビピリジン、およびDABCO錯体はチャンネル構造を持つ三次元の無限格子構造を有し、これらのチャンネル内部は二次元シート状の(+)-樟脳酸部位によりホモキラルな環境となっている。また、いずれの錯体も、その細孔はバルクでもホモキラルである。(+)-樟脳酸は容易に入手できる光学活性ジカルボン酸であるが、直線構造ではないため、その遷移金属塩の結晶構造を予測しにくい。剛直で直線状の光学活性ジカルボン酸を使えばナノ細孔の精密分子設計が可能になると期待できる。剛直な直線構造と不斉を両立させるために、軸不斉カルボン酸を考え、また、触媒性官能基となりうるフェノール性ヒドロキシ基を有するビナフトールを基本骨格として用いることにした。(S)-ビナフトールを原料として用い、4段階で4,4′-位をジブロモ化した。この直接カルボキシかを検討したが、ブチルリチウムで処理すると分解したため、鈴木-宮浦反応あるいはStille反応でビニル化した後、酸化して直線構造を有する軸不斉カルボン酸を得た。一方、光学活性アレン-1,3-ジカルボン酸の合成も検討した。アレン-1,3-ジカルボン酸を3-ブチン-1-オールから2段階で合成し、キニーネによる光学分割を検討したが、アレン-1,3-ジカルボン酸は熱的に不安定性で分解してしまった。そこで、アセトン-1,3-ジカルボン酸エチルから2段階でアレン-1,3-ジカルボン酸のメンチルエステルを合成し、そのジアステレオマー分離を経て光学活性なアレン-1,3-ジカルボン酸を得た。さらに、直線構造を有してはいないものの、軸不斉を有するジカルボン酸として2,2′-ジヒドロキシ-1,1′-ビナフチル-3,3′-ジカルボン酸を用いて銅塩を作成した。ラセミのジカルボン酸を用いたところ、二次元無限シート構造を有し、細孔を持つ結晶が得られた。それぞれのシートはホモキラルであった。細孔径は4.4Åであり、単結晶X線構造解析の結果とよく一致した。

Report

(2 results)
  • 2007 Annual Research Report
  • 2006 Annual Research Report
  • Research Products

    (25 results)

All 2007 2006

All Journal Article (19 results) (of which Peer Reviewed: 7 results) Presentation (2 results) Book (4 results)

  • [Journal Article] Synthesis and Properties of Nylon-0,2 Oxidatively Degradable polymer That is Stable in Air2007

    • Author(s)
      Nobuhiro Kihara, Rie Ii, Akiya Ogawa
    • Journal Title

      J. Polym. Sci., Part A: Polym. Chem. 45(5)

      Pages: 963-967

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Solvent-Free Synthesis of Pseudopolyrotaxane and Polyrotaxane: Efficient Threading Complexation of a Cyclodextrin Wheel and a Linear Polymer Axle to Yield Pseudopolyrotaxane and Its Fixation to Polyrotaxane by the Direct Grinding of a Solid Mixture.2007

    • Author(s)
      Runtao Liu, Takeshi Maeda, Nobuhiro Kihara, Akira Harada, Toshikazu Takata
    • Journal Title

      J. Polym. Sci., Part A: Polym. Chem. 45(8)

      Pages: 1571-1574

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Lewis acid-catalyzed reduction of dithioacetals by 1,4-cyclohexadiene2007

    • Author(s)
      Kei-ichiro Ikeshita, Nobuhiro Kihara, Motohiro Sonoda, and Akiya Ogawa
    • Journal Title

      Tetrahedron Lett. 48(17)

      Pages: 3025-3028

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Reaction of Copper(II)Complexes with Na_2S_2. An Alternative Method for the Preparation of Disulfido-Dicopper(II)Complexes.2007

    • Author(s)
      Masayuki Inosako, Chizu Shimokawa, Hideki Sugimoto, Nobuhiro Kihara, Toshikazu Takata, and Shinobu Itoh
    • Journal Title

      Chem. Lett. 36(11)

      Pages: 1306-1307

    • NAID

      10019791936

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Poly[2]rotaxane by Sonogashira Polycondensation2007

    • Author(s)
      Hisahiro Sasabe, Norihiro Inomoto, Nobuhiro Kihara, Yuichi Suzuki, Akiya Ogawa, Toshikazu Takata
    • Journal Title

      J. Polym. Sci 45(17)

      Pages: 4154-4160

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Oxidation Catalysis of Microporous Metal Carboxylate Complexes2007

    • Author(s)
      C. N. Kato, W. Mori
    • Journal Title

      C. R. Chim 10

      Pages: 284-294

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hydrogen Adsorption Properties of a Novel Lantern-type Dinuclear Co(BDC)(DABCO)1/2.2007

    • Author(s)
      T. Takei, T. Ii, J. Kawashima, T. Ohmura, M. Ichikawa, M. Hosoe, Y. Hinya, I. Kanoya and W. Mori
    • Journal Title

      Chem. Lett. 36

      Pages: 1136-1136

    • NAID

      10019845755

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Asymmetric Synthesis and Optical Resolution of Planar Chiral Rotaxane2007

    • Author(s)
      Y.Makita et al.
    • Journal Title

      Chemistry Letters 36・1

      Pages: 162-163

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Effect of Steric Barrier on the Shuttling of Rotaxane Having Crown Ether Wheel2007

    • Author(s)
      N.Kihara et al.
    • Journal Title

      Chemistry Letters 36・2

      Pages: 208-209

    • NAID

      10018522067

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Synthesis and Properties of Nylon-0,2 - Oxidatively Degradable polymer That is Stable in Air2007

    • Author(s)
      N.Kihara et al.
    • Journal Title

      Journal of Polymer Science Part A : Polymer Chemistry 45・5

      Pages: 963-967

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Tributylphosphane-catalyzed Condensation of Alcohol and Carboxylic Acid with DCC Directed toward Rotaxane Synthesis2007

    • Author(s)
      Y.Makita et al.
    • Journal Title

      Chemistry Letters 36・1

      Pages: 102-103

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Rotaxane synthesized by end-capping via hydroruthenation of axle terminal acetylene and its derivation to...2006

    • Author(s)
      H.Sasabe et al.
    • Journal Title

      Chemistry Letters 35・2

      Pages: 212-213

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Transition-metal-catalyzed carbonylation of allenes with carbon monoxide and thiols2006

    • Author(s)
      M.Kajitani et al.
    • Journal Title

      Tetrahedron 62・26

      Pages: 6355-6360

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Sequential 0- and N-Acylation Protocol for High-Yield Preparation and Modification of Rotaxanes :...2006

    • Author(s)
      Y.Tachibana et al.
    • Journal Title

      Journal of Organic Chemistry 71・14

      Pages: 5093-5104

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Photoinduced electron transfer processes in three component rotaxanes with porphyrins, [60]fullerene and triphenylamine2006

    • Author(s)
      H.Sasabe et al.
    • Journal Title

      Journal of Porphyrins and Phthalocyanines 10・12

      Pages: 1346-1359

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Photoinduced electron transfer processes in rotaxanes containing [60]fullerene and ferrocene2006

    • Author(s)
      A.S.D.Sandanayaka et al.
    • Journal Title

      Australian Journal of Chemistry 59・3

      Pages: 186-192

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Synthesis of [60]fullerene-functionalized rotaxanes2006

    • Author(s)
      H.Sasabe et al.
    • Journal Title

      Tetrahedron 62・9

      Pages: 1988-1997

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Synthesis structures and characterization of the dinuclear nickel(II) complexes containing N,N,N',N'- tetrakis[(1-ethyl-2-benzimidazolyl)methyl]-2-hyd roxy-1,3-diaminopropane and an azide ion2006

    • Author(s)
      Tomohiko Sato, Wasuke Mori, Yong Xie, Nobuko Kanehisa, Yasushi Kai, Mie Fujii, Shoko Goto, Emi Nagai, Yasuo Nakao
    • Journal Title

      Inorganica Chimica Acta 359

      Pages: 2271-2274

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Room temperature oxidation of alcohols with 1 atm dioxygen and air catalyzed by a novel three-dimensional microporus ruthenium(II, III) 4, 4', 4 ', 4''' -(21H, 23H-porphine-5, 10, 20-tetrayl)...2006

    • Author(s)
      C, N, Kato, M.Ono, T.Ohmura, W.Mori
    • Journal Title

      Catalysis Comm 7

      Pages: 673-677

    • Related Report
      2006 Annual Research Report
  • [Presentation] Construction of Nanoporous Materials Functionalized by Axial Chirality2007

    • Author(s)
      A. Narita, Y. Taguchi, H. Yasutake, N. Kihara, W. Mori
    • Organizer
      Third International Symposium on Chemistry of Coordination Space
    • Place of Presentation
      日本・兵庫県
    • Related Report
      2007 Annual Research Report
  • [Presentation] Novel Fabrication of Mesoporous Silicates Derived by Copper (II)Carboxylate Templates.2007

    • Author(s)
      K.Kitashiro, M. Ichikawa, W. Mori
    • Organizer
      Third International Symposium on Chemistry of Coordination Space
    • Place of Presentation
      日本・兵庫県
    • Related Report
      2007 Annual Research Report
  • [Book] 三共出版2007

    • Author(s)
      木原 伸浩、高田 十志和、早下 隆士・築部 浩編著
    • Publisher
      超分子マシーンへのアプローチ、分子認識と超分子
    • Related Report
      2007 Annual Research Report
  • [Book] Redox Systems under Nano-Space Control2006

    • Author(s)
      N.Kihara et al.
    • Total Pages
      18
    • Publisher
      Springer
    • Related Report
      2006 Annual Research Report
  • [Book] 接着とはく離のための高分子-開発と応用-2006

    • Author(s)
      木原 伸浩
    • Total Pages
      12
    • Publisher
      CMC
    • Related Report
      2006 Annual Research Report
  • [Book] よくわかる有機化学の基本と仕組み2006

    • Author(s)
      木原 伸浩
    • Total Pages
      350
    • Publisher
      秀和システム
    • Related Report
      2006 Annual Research Report

URL: 

Published: 2006-04-01   Modified: 2018-03-28  

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