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2006 Fiscal Year Final Research Report Summary

Synthesis of Novel BINAP derivatives and their application

Research Project

Project/Area Number 17550111
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionNara National College of Technology

Principal Investigator

SHIMADA Toyoshi  Nara National College of Technology, Department of Chemical Engineering, Professor, 物質化学工学科, 教授 (20303802)

Project Period (FY) 2005 – 2006
KeywordsBINAP / Iodination / Axial Chirality / Cross-Coupling / Catalytic Asymmetric Synthesis / Fluorescence / Phenylene-ethynylene
Research Abstract

One of the most useful chiral phosphine ligands is 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), which exhibits high enantioselectivity in several types of asymmetric reactions including ruthenium-catalyzed hydrogenation and rhodium-catalyzed 1,4-addition and its related reactions. Over the last decade, there have been major efforts to prepare BINAP derivatives for recycling catalytic systems and achieving higher selectivity in asymmetric synthesis. Most of these BINAP derivatives have been prepared in several steps starting from 6-or 6,6'-substituted 1,1'-bi-2-naphthol. However, these derivatizations are inferior to direct functionalization of BINAP due to their low yields and associated handling losses. Here we report a new facile regioselective iodination at the 5,5'-position of BINAP and subsequent Sonogashira coupling reaction leading to the ethynyl-BINAP which is useful as a chiral ligand for a rhodium-catalyzed asymmetric 1,4-addition. Bis(pyridine)iodonium tetrafluoroborate was successfully used for regioselective iodination of BINAP dioxide to give 5,5'-diiodoBINAP dioxide in excellent yield of 92%, with no observed formation of 4,4'-diiodoBINAP dioxide. A Sonogashira cross-coupling reaction with 5,5'-diiodoBINAP dioxide gave the desired bis(phenylene-ethynylene) products in good yield. The resulting 5,5'-disubstituted BINAP dioxides have excellent fluorescent properties. Furthermore, we examined to transform 5,5'-disubstituted BINAP dioxides to sol-gel precursors with allylsilyl groups giving chirally photochemical materials. It is confidently expected that these chiral sol-gel precursors open the new field of material chemistry.

  • Research Products

    (12 results)

All 2007 2006 2005

All Journal Article (10 results) Book (1 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Cubic phenylene bridged mesoporous hybrids from allylorganosilane precursors and their applications in Friedel-Crafts acylation reaction2007

    • Author(s)
      Toyoshi Shimada et al.
    • Journal Title

      Microporous and Mesoporous Materials 101

      Pages: 231

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Cubic phenylene bridged mesoporous hybrids from allylorganosilane precursors and their applications in Friedel-Crafts acylation reaction.2007

    • Author(s)
      Kapoor, M.P., Kasama, Y., Yokoyama, T., Yanagi, M., Yokoyama, T., Inagaki, S., Shimada, T., Nanbu, H., Juneja, L.R.
    • Journal Title

      Microporous Mesoporous Mater. 101

      Pages: 231-239

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] A useful procedure for diiodination of carbazoles and subsequent efficient transformation to novel 3,6-bis(triethoxysilyl) carbazoles giving mesoporous materials2006

    • Author(s)
      Toyoshi Shimada et al.
    • Journal Title

      Tetrahedron Letters 47

      Pages: 6957

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Rhodium-Catalyzed Asymmetric Synthesis of Indanones : Development of a New "Axially Chiral" Bisphosphine Ligand2006

    • Author(s)
      Toyoshi Shimada et al.
    • Journal Title

      Jornal of the American Chemical Society 128

      Pages: 2772

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Self-assembly of cubic phenylene bridged mesoporous hybrids from allylorganosilane precursors2006

    • Author(s)
      Toyoshi Shimada et al.
    • Journal Title

      Journal of Materials Chemistry 16

      Pages: 3305

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] A useful procedure for diiodination of carbazoles and subsequent efficient transformation to novel 3,6-bis(triethoxysilyl)carbazoles giving mesoporous materials.2006

    • Author(s)
      Y.Maegawa, Y.Goto, S.Inagaki, T.Shimada
    • Journal Title

      Tetrahedron Lett. 47

      Pages: 6957-6960

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Rhodium-Catalyzed Asymmetric Synthesis of Indanones : Development of a New "Axially Chiral" Bisphosphine Ligand.2006

    • Author(s)
      Shintani, R., Yashio, K., Nakamura, T., Okamoto, K., Shimada, T., Hayash, T.
    • Journal Title

      J.Am.Chem.Soc. 128

      Pages: 2772-2773

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Self-assembly of cubic phenylene bridged mesoporous hybrids from allylorganosilane precursors.2006

    • Author(s)
      Kapoor, M.P., Kasama, Y., Yokoyama, T., Yanagi, M., Inagaki, S., Shimada, T., Nanbu, H., Juneja, L.
    • Journal Title

      R.J.Mater.Chem. 48

      Pages: 4714-4722

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Facile Preparation of a New BINAP-based Building Block, 5,5'-diiodoBINAP, and its Synthetic Application2005

    • Author(s)
      Toyoshi Shimada et al.
    • Journal Title

      Journal of Organic Chemistry 70

      Pages: 10178

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Facile Preparation of a New BINAP-based Building Block, 5,5'-diiodoBINAP, and its Synthetic Application.2005

    • Author(s)
      Shimada, T., Suda, M., Nagano, T., Kakiuchi, K.
    • Journal Title

      J.Org.Chem. 70

      Pages: 10178-10181

    • Description
      「研究成果報告書概要(欧文)」より
  • [Book] ケイ素化合物の選定と最適利用技術-応用事例集-2006

    • Author(s)
      嶋田豊司 他
    • Total Pages
      524
    • Publisher
      (株)技術情報協会
    • Description
      「研究成果報告書概要(和文)」より
  • [Patent(Industrial Property Rights)] ビナフチル誘導体およびその製造方法2005

    • Inventor(s)
      嶋田豊司, 垣内喜代三
    • Industrial Property Rights Holder
      奈良先端科学技術大学院大学
    • Industrial Property Number
      特願2005-262628
    • Filing Date
      2005-09-09
    • Description
      「研究成果報告書概要(和文)」より

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Published: 2008-05-27  

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