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Organic Synthesis in Water Utilizing Inorganic Porous Materials

Research Project

Project/Area Number 15350057
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionOsaka University

Principal Investigator

MINAKATA Satoshi  Osaka University, Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (90273599)

Co-Investigator(Kenkyū-buntansha) KOMATSU Mitsuo  Osaka University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (60029197)
ODERAOTOSHI Yoji  Osaka University, Graduate School of Engineering, Assistant Professor, 大学院・工学研究科, 助手 (60324810)
Project Period (FY) 2003 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥14,700,000 (Direct Cost: ¥14,700,000)
Fiscal Year 2005: ¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2004: ¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2003: ¥7,700,000 (Direct Cost: ¥7,700,000)
KeywordsGreen Chemistry / Environmentally Organic Synthesis / Organic Synthesis in Water / Inorganic Porous Materials / Silica Gel / Aziridines / Water Soluble Nucleophiles / Ring Opening Reaction / チアゾリジン / 水 / MCM-41 / オレフィン / クロラミンT
Research Abstract

Although the use of PTC to permit the reaction in aqueous media is a general method, an alternative potential process in water was devised, based on the adsorptive nature of silica gel. While the application of silica gel to organic synthesis has been widely investigated, its use in organic reactions in aqueous media has not been exploited, to the best of our knowledge. Silica would be effective as organic reaction media in water because the organic molecule as a substrate would be adsorbed to the silica by hydrophobic interactions between the surface of the silica and the organic molecule. We investigated here on the iodine-catalyzed aziridination of olefins using Chloramine-T (CT) and the ring opening of the resulting aziridine in a silica-water system, in which the use of silica (silica gel vs. MCM-41) showed unique results. For example, when styrene was treated with CT, K_2CO_3, and a catalytic amount of I_2 in the presence of Silica Gel 60 in water, N-(p-toluenesulfonyl)-2-phenylaziridine was obtained in good yield. A variety of olefins were successfully employed in this silica-mediated olefin aziridination in water using the iodine catalyst-CT system. To show the generality of the present media in organic synthesis, the ring opening of N-(p-toluenesulfonyl)-2-n-hexylaziridine with NaN_3 or KCN was examined. The reaction of aziridines with NaN_3 or KCN in water in the absence of silica did not proceed similarly to the case of the aziridination described above. When Silica Gel 60 was added, however, the desired reaction proceeded to afford the regioselective ring-opening products, respectively. To obtain a ring expansion product by the system, potassium thiocyanate was employed in the reaction. As was expected, a ring expansion product, thiazolidine derivative consisting of one thiocyanate and two aziridines moieties was produced in good yield as a mixture of two diastereomers.

Report

(4 results)
  • 2005 Annual Research Report   Final Research Report Summary
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (22 results)

All 2006 2005 2004 2003 Other

All Journal Article (20 results) Publications (2 results)

  • [Journal Article] A Facile [4+1] Type Synthetic Route to Thiophenes from Dienol Silyl Ethers and Elemental Sulfur2006

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Tetrahedron 62・4

      Pages: 537-542

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Unprecedented 1,4-Stannatropy : Effective Generation of Azomethine Ylides as Nitrile Ylide Equivalents from N-(Stannyl)thioamides2006

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Chemical Communications 5

      Pages: 526-528

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Unprecedented CO_2-Promoted Aminochlorination of Olefines with Chloramine-T2006

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Organic Letters 8・5

      Pages: 967-969

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Unprecedented 1,4-Stannatropy : Effective Generation of Azomethine Ylides as Nitrile Ylides Equivalents from N-(Stannyl)thioamides2006

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Chemical Communications 5

      Pages: 526-528

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Unprecedented CO_2-Promoted Aminochlorination of Olefines with Chloramine-T2006

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Organic Letters 8(5)

      Pages: 967-969

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Unprecedented 1,4-Stannatropy : Effective Generation of Azomethine Ylides as Nitrile Ylide Equivalents from N-(Stannyl) thioamides2006

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Chemical Communications 5

      Pages: 526-528

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Lewis Base Catalyzed Ring Opening of Aziridines with Silylated Nucleophiles2005

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Organic Letters 7・16

      Pages: 3509-3512

    • NAID

      130006997024

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Novel Synthesis of gem-Dichloroaziridines from Imines via the KF/Al_2O_3-Promoted Generation of Dichlorocarbene from Chloroform2005

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Journal of Organic Chemistry 70・13

      Pages: 5320-5322

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Silica Gel-Promoted Synthesis of 3,4,5-Triaryltetrahydro-1,4-thiazine Derivatives from β,β'-Dichloro Sulfides and Aromatic Amines2005

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Tetrahedron Letters 46・47

      Pages: 8105-8108

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Lewis Base Catalyzed Ring Opening of Aziridines with Silylated Nucleophiles2005

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Organic Letters 7(16)

      Pages: 3509-3512

    • NAID

      130006997024

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Novel Synthesis of gem-Dichloroaziridines from Imines via the KF/Al_2O_3-Promoted Generation of Dichlorocarbene from Chloroform2005

    • Author(s)
      Satoshi Minakata
    • Journal Title

      The Journal of Organic Chemistry 70(13)

      Pages: 5320-5322

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Silica Gel-Promoted Synthesis of 3,4,5-Triaryltetrahydro-1,4-thiazine Derivatives from Dichloro Sulfides and Aromatic Amines2005

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Tetrahedron Letters 46(47)

      Pages: 8105-8108

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] A Facile [4+1] Type Synthetic Route to Thiophenes from Dienol Silyl Ethers and Elemental Sulfur2005

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Tetrahedron 62(4)

      Pages: 537-542

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Silica-Water Reaction Media Its Application to the Formation and Ring Opening of Aziridines2004

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Angewand to Chemie International Edition 43・1

      Pages: 79-81

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Silica-Water Reaction Media : Its Application to the Formation and Ring Opening of Aziridines2004

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Angewandte Chemie International Edition 43(1)

      Pages: 79-81

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Silica-Water Reaction Media : Its Application to the Formation and Ring Opening of Aziridines2004

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Angewandte Chemie Itnernational Edition 43,1

      Pages: 79-81

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Development of New Synthetic Methods of Heterocycles Using Chloramine-T as a Nitrogen Source2003

    • Author(s)
      Satoshi Minakata
    • Journal Title

      J.Synth.Org.Chem. 61・7

      Pages: 706-714

    • NAID

      10011906937

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Introduction of an N1 Unit to Monoenes or 1,6-Dienes Using Chloramine-T-Silver Nitrate a New Route to Aziridines or Bicyclic Pyrrolidines2003

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Heterocycles 60・2

      Pages: 289-298

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Development of New Synthetic Methods of Heterocycles Using Chloramine-T as a Nitrogen Source2003

    • Author(s)
      Satoshi Minakata
    • Journal Title

      J.Synth.Org.Chem. 61(7)

      Pages: 706-714

    • NAID

      10011906937

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Introduction of an N1 Unit to Monoenes or 1,6-Dienes Using Chloramine-T-Silver Nitrate : a New Route to Aziridines or Bicyclic Pyrrolidines2003

    • Author(s)
      Satoshi Minakata
    • Journal Title

      Heterocycles 60(2)

      Pages: 289-298

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Publications] Satoshi Minakata: "Development of New Synthetic Methods of Heterocycles Using Chloramine-T as a Nitrogen Source"J.Synth.Org.Chem.. 61・7. 706-714 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Satoshi Minakata: "Introduction of an NI Unit to Monoenes or 1,6-Dienes Using Chloramine-T-Silver Nitrate : a New Route to Aziridines or Bicyclic Pyrrolidines"Heterocycles. 60・2. 289-298 (2003)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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