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2014 Fiscal Year Annual Research Report

超原子価ヨウ素触媒を用いる環境低負荷型有機変換反応

Research Project

Project/Area Number 24245020
Research InstitutionNagoya University

Principal Investigator

石原 一彰  名古屋大学, 工学(系)研究科(研究院), 教授 (40221759)

Project Period (FY) 2012-04-01 – 2016-03-31
Keywords酸化的カップリング / 触媒 / ヨウ素 / 超原子価 / 次亜ヨウ素酸塩 / 次亜塩素酸塩 / 不斉触媒 / 脱芳香族化反応
Outline of Annual Research Achievements

酸化的カップリング反応を触媒する遷移金属や重金属の多くはレアメタルであり、毒性も懸念されることから、代替元素としてヨウ素が注目されている。日本のヨウ素の生産量は世界第2位であり、資源小国の日本にとって貴重な資源である。また、ヨウ素はヒトの必須元素であり、安全性も高い。本研究課題では、ヨウ素の超原子価の特徴を活かし、ヨウ素化合物を有機分子触媒に用いる環境調和型酸化的カップリング反応の開発及び不斉超原子価ヨウ素触媒の開発を目的とし研究を遂行した。触媒前駆体にはヨードアレンまたは第四級アンモニウムヨージドを、共酸化剤には過酸化水素や過酸化アルコールを用い、反応系に一切の毒性の強い物質を用いない。触媒前駆体にはヨードアレンあるいは第四級アンモニウムヨージドを用いた。具体的な研究実績としては、(1) ortho-キノンメチドの新規酸化的生成及びタンデム型反応への応用、(2) IBS触媒を用いるフェノール類のレジオ選択的酸化反応とその合成的応用、(3) キラル超原子価ヨウ素(III)触媒によるビアリールヒドロキシカルボン酸類の酸化的速度論的光学分割、(4) キラル超原子価ヨウ素(III)触媒を用いる1,4-ヒドロキノン誘導体のエナンチオ選択的酸化的脱芳香族化反応、(5) キラル次亜ヨウ素酸塩触媒を用いるエナンチオ選択的酸化的エーテル環化反応、(6) キラル次亜ヨウ素酸塩触媒を用いるインドール類のエナンチオ選択的酸化的脱芳香族化反応、(7) キラル次亜ヨウ素酸塩触媒を用いるエナンチオ選択的酸化的環化反応とその反応機構の解明、(8) 次亜ヨウ素酸塩触媒を用いるカルボニル化合物の酸化的α-アジド化反応、(9) 次亜塩素酸ナトリウム五水和物を用いるカルボニル化合物の触媒的α-塩素化反応、がある。

Research Progress Status

27年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

27年度が最終年度であるため、記入しない。

  • Research Products

    (16 results)

All 2016 2015 2014 Other

All Int'l Joint Research (1 results) Journal Article (6 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 6 results,  Acknowledgement Compliant: 5 results) Presentation (7 results) (of which Int'l Joint Research: 7 results,  Invited: 7 results) Remarks (1 results) Patent(Industrial Property Rights) (1 results)

  • [Int'l Joint Research] ICIQ(イタリア)

    • Country Name
      ITALY
    • Counterpart Institution
      ICIQ
  • [Journal Article] Structurally defined molecular hypervalent iodine catalysts for intermolecular enantioselective reactions2016

    • Author(s)
      Stefan Haubenreisser, Thorsten H. Wöste, Claudio Martínez, Kazuaki Ishihara, Kilian Muñiz
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 55 Pages: 413-417

    • DOI

      10.1002/anie.201507180

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Chiral ammonium hypoiodite salt-catalyzed enantioselective oxidative cycloetherification to 2-acyl tetrahydrofurans2016

    • Author(s)
      Muhammet Uyanik, Hiroki Hayashi, Hirokazu Iwata, Kazuaki Ishihara
    • Journal Title

      Chem. Lett.

      Volume: 45 Pages: 353-355

    • DOI

      10.1246/cl.160004

    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Chiral ammonium hypoiodite-catalyzed enantioselective oxidative dearomatization of 1-naphthols using hydrogen peroxide2015

    • Author(s)
      Muhammet Uyanik, Niiha Sasakura, Erina Kaneko, Kento Ohori, Kazuaki Ishihara
    • Journal Title

      Chem. Lett.

      Volume: 44 Pages: 179-181

    • DOI

      10.1246/cl.141012

    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Practical oxidative dearomatization of phenols with sodium hypochlorite pentahydrate2015

    • Author(s)
      Muhammet Uyanik, Niiha Sasakura, Mitsuyoshi Kuwahata, Yasukazu Ejima, Kazuaki Ishihara
    • Journal Title

      Chem. Lett.

      Volume: 44 Pages: 381-383

    • DOI

      10.1246/cl.141130

    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] High-performance hypoiodite/hydrogen peroxide catalytic system for the oxylactonization of aliphatic γ-oxocarboxylic acids2015

    • Author(s)
      Muhammet Uyanik, Daisuke Suzuki, Mizu Watanabe, Hiroyasu Tanaka, Kikuo Furukawa, Kazuaki Ishihara
    • Journal Title

      Chem. Lett.

      Volume: 44 Pages: 387-389

    • DOI

      10.1246/cl.141110

    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] High-turnover hypoiodite catalysis for asymmetric synthesis of tocopherols2014

    • Author(s)
      Muhammet Uyanik, Hiroki Hayashi, Kazuaki Ishihara
    • Journal Title

      Science

      Volume: 345 Pages: 291-294

    • DOI

      10.1126/science.1254976

    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Enantioselective iodocyclization induced by chiral base–acid cooperative catalysis2015

    • Author(s)
      Kazuaki Ishihara, Hidefumi Nakatsuji
    • Organizer
      Pacifichem 2015
    • Place of Presentation
      Honolulu, Hawai, USA
    • Year and Date
      2015-12-15 – 2015-12-20
    • Int'l Joint Research / Invited
  • [Presentation] Rational Design of Chiral Acid–Base Combined Catalysts2015

    • Author(s)
      Kazuaki Isihara
    • Organizer
      14th Symposium on Chemical Approach to Chirality
    • Place of Presentation
      Kagurazaka, Tokyo
    • Year and Date
      2015-11-18 – 2015-11-18
    • Int'l Joint Research / Invited
  • [Presentation] Enantioselective halocyclizations induced by chiral base–acid cooperarive catalysis2015

    • Author(s)
      Kazuaki Isihara
    • Organizer
      HALCHEM VII (7th International Meeting on Halogen Chemistry)
    • Place of Presentation
      the Jan Długosz University in Częstochowa, Poland
    • Year and Date
      2015-09-03 – 2015-09-06
    • Int'l Joint Research / Invited
  • [Presentation] Catalytic enantioselective cyclization reaction to construct chroman skeletons2014

    • Author(s)
      Kazuaki Isihara
    • Organizer
      The 9th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-9)/The 5th New Phase International Conference on Cutting-Edge Organic Chamistry in Asia (NICCEOCA-5)
    • Place of Presentation
      Eastin Hotel Petaling Jaya, Malaysia
    • Year and Date
      2014-12-01 – 2014-12-04
    • Int'l Joint Research / Invited
  • [Presentation] The Development of Catalytic Enantioselective Cyclizations Based on Iodine Chemistry2014

    • Author(s)
      Kazuaki Isihara
    • Organizer
      AbbVie lecture
    • Place of Presentation
      The University of Illinois at Urabana-Champaign, USA
    • Year and Date
      2014-09-25 – 2014-09-25
    • Int'l Joint Research / Invited
  • [Presentation] Catalytic Enantioselective Iodolactonization of 4-Substituted 4-Pentenoic Acids Promoted through Halogen Bonding2014

    • Author(s)
      Kazuaki Isihara
    • Organizer
      1st International Symposium on Halogen Bonding (ISXB-1)
    • Place of Presentation
      Porto Cesareo, Italy
    • Year and Date
      2014-06-18 – 2014-06-22
    • Int'l Joint Research / Invited
  • [Presentation] Stereoselective halocyclization Catalyzed by Chiral Lewi Bases2014

    • Author(s)
      Kazuaki Isihara
    • Organizer
      The 6th ORCA Meeting (The 6th Organocatalysis Meeting)
    • Place of Presentation
      Palermo, Italy
    • Year and Date
      2014-05-07 – 2014-05-10
    • Int'l Joint Research / Invited
  • [Remarks] 石原一彰研究室ーISHIHARA GROUP

    • URL

      http://www.ishihara-lab.net

  • [Patent(Industrial Property Rights)] 新規なアルキルカルボニルラクトン化合物及びその製造方法2014

    • Inventor(s)
      石原一彰、Muhammet Uyanik、古川喜久夫、田中博康
    • Industrial Property Rights Holder
      国立大学法人名古屋大学
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2014-204756
    • Filing Date
      2014-10-03

URL: 

Published: 2017-01-06  

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