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超原子価ヨウ素化合物の化学的研究

Research Project

Project/Area Number 18790009
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeSingle-year Grants
Research Field Chemical pharmacy
Research InstitutionOsaka University

Principal Investigator

土肥 寿文  Osaka University, 薬学研究科, 助教 (50423116)

Project Period (FY) 2006 – 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2007: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 2006: ¥2,100,000 (Direct Cost: ¥2,100,000)
Keywords有機ヨウ素 / 酸化 / リサイクル / 環境対応 / 有機触媒 / 構造・機能材料 / 複素環化合物 / 選択的合成
Research Abstract

本年度は昨年度に引き続き、ヘテロ芳香族化合物に対する新規な反応性の開拓をphenyliodine diacetate(PIDA)とphenyliodine bis(trifiuoroacetate)(PIEA)を中心に用い、検討を行なった。さらに、得られた成果を独自のリサイクル・触媒的利用・不斉反応へと応用することで、環境面や実用性にも配慮した方法論へと発展させた。
1.PIEAを用いるピロール類の2量化反応で、置換基や用いるルイス酸をうまく選択することで、染料やポルフィリン、有機材料の基本骨格に見られるビピロール類の種々位置異性体の作りわけに成功した。また、PIEAによる芳香族化合物の一電子酸化の起こり易さが酸化電位に支配されないことに注目し、メシチレンを求核剤とする効果的な芳香族化合物の酸化的直接クロスカップリング法を開発した。本法は、官能基化や遷移金属触媒による活性化を一切必要としない、類例のない直接的ビアリール合成法である。
2.溶媒効果を利用した、材料科学の領域で有用なジアリールヨードニウム塩型化合物の緩和な条件下、水のみを副産物とする環境調和型新規直接合成法の開発に成功した。
3.超原子価ヨウ素反応剤の活性化剤を種々検討している際に、KBrを用いると芳香環の酸化は起こらず、代わりに飽和C-H結合の酸化が起こる興味深い現象を見出した。本結果を応用し、飽和C-H結合の活性化を含む官能基化を必要としない直接的アリ「ルラクトン類の合成法を開発した。
4.超原子価ヨウ素反応剤の触媒的利用法の概念をさらに展開し、世界で初めてとなる触媒的C-N、およびC-C結合形成反応へと発展させた。また、不斉反応に有望な新規キラル化合物を設計し、フェノール類の高選択的な不斉酸化の実現に成功した。
5.上記の研究に独自に開発した多点型リサイクル反応剤を組み込み、環境対応型の合成反応へと改良を行った。

Report

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

    (27 results)

All 2008 2007 2006

All Journal Article (16 results) (of which Peer Reviewed: 7 results) Presentation (10 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Oxidative Cross-Coupling of Arenes Induced by Single-Electron Transfer Leading to Biaryls by Use of Organoiodine (III) Oxidants2008

    • Author(s)
      Dohi, Toshifumi, et. al.
    • Journal Title

      Angew. Chem. Int. Ed. 47

      Pages: 1301-1304

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A New Chiral Hypervalent Iodine (III) Reagent for Enantioselective Dearomatization of Phenols2008

    • Author(s)
      Dohi, Toshifumi, et. al.
    • Journal Title

      Angew. Chem. Int. Ed. 47(印刷中)

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] First H5rpervalent Iodine (III)-Catalyzed C-N Bond Forming Reaction: Catalytic Spirocyclization of Amides to N-Fused Spirolactams2007

    • Author(s)
      Dohi, Toshifumi, et. al.
    • Journal Title

      Chem. Commun.

      Pages: 1124-1126

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Direct Lactorie Formation by Using Hypervalent Iodine (III) Reagents with KBr via Selective C-H Abstraction Protocol2007

    • Author(s)
      Dohi, Toshifumi, et. al.
    • Journal Title

      Org. Lett. 9

      Pages: 3129-3132

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Versatile Direct Dehydrative Approach for Diaryliodonium (III) Salts in Fluoroalcohol Media2007

    • Author(s)
      Dohi, Toshifumi, et. al.
    • Journal Title

      Chem. Commun.

      Pages: 4152-4154

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Total Synthesis of (±)-γ-Rubromycin on the Basis of Two Aromatic Pummerer-Type Peactions2007

    • Author(s)
      Dohi, Toshifumi, Kita Yasuyuki, et. al.
    • Journal Title

      Angew. Chem. Int. Ed. 46

      Pages: 7458-7461

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Regioselective Bipyrrole Coupling of Pyrroles and 3-Substituted Pyrroles Using Phenyliodine(III) Bis (trifluoroacetate)2007

    • Author(s)
      Dohi, Toshifumi, et. al.
    • Journal Title

      Synthesis

      Pages: 2913-2919

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Direct Cyanation of Heteroaromatic Compounds Mediated by Hypervalent Iodine(III)Reagents; In Situ Generation of phI(III)-CN Species and Their Cyano Transfer2007

    • Author(s)
      Dohi, Toshifumi, et. al.
    • Journal Title

      J. Org. Chem. 72・1

      Pages: 109-116

    • Related Report
      2006 Annual Research Report
  • [Journal Article] First Hypervalent Iodine(III)-Catalyzed C-N Bond Forming Reaction: Catalytic Spirocyclization of Amides to N-Fused Spirolactams2007

    • Author(s)
      Dohi, Toshifumi, et. al.
    • Journal Title

      Chem. Commun. 12

      Pages: 1224-1226

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Regioselective Bipyrrole Coupling of Pyrroles and 3-Substituted Pyrroles Using Phenyliodine(III)Bis(trifluoroacetate)2007

    • Author(s)
      Dohi, Toshifumi, et. al.
    • Journal Title

      Synthesis (印刷中)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Direct Lactone Formation by Using Hypervalent Iodine(III)Reagents with KBr via Selective C-H Abstraction Protocol2007

    • Author(s)
      Dohi, Toshifumi, et. al.
    • Journal Title

      Org. Lett. 9・(印刷中)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] The First Total Synthesis of(±)-Y-Rubromycin via Double Aromatic Pummerer-Type Reactions2007

    • Author(s)
      Dohi, Toshifumi, Kita Yasuyuki, et. al.
    • Journal Title

      Angew. Chem. Int. Ed. 46・(印刷中)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Versatile Direct Dehydrative Approach for Diaryliodonium(III)Salts in Fluoroalcohol Media2007

    • Author(s)
      Dohi, Toshifumi, et. al.
    • Journal Title

      Chem. Commun. (印刷中)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Direct Synthesis of Bipyrroles Using Phenyliodine Bis(trifluoroacetate)with Bromotrimethylsilane2006

    • Author(s)
      Dohi, Toshifumi, et. al.
    • Journal Title

      Org. Lett. 8・10

      Pages: 2007-2010

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Development of environmentally benign oxidations using hypervalent iodine(III)reagents2006

    • Author(s)
      Dohi, Toshifumi
    • Journal Title

      Yakugaku Zasshi 126・9

      Pages: 757-766

    • NAID

      110006154986

    • Related Report
      2006 Annual Research Report
  • [Journal Article] A Facile and Clean Direct Cyanation of Heteroaromatic Compounds Using a Recyclable Hypervalent Iodine(III)Reagent2006

    • Author(s)
      Dohi, Toshifumi, et. al.
    • Journal Title

      Chem. Pharm. Bull. 54・12

      Pages: 1608-1610

    • NAID

      110004836487

    • Related Report
      2006 Annual Research Report
  • [Presentation] Development of Oxidative Lactone Forming Reaction at Benzyl Positions Using Hypervalent Iodine (III) Reagent2007

    • Author(s)
      土肥寿文 他
    • Organizer
      第10回 ヨウ素学会シンポジウム
    • Place of Presentation
      千葉
    • Year and Date
      2007-11-16
    • Related Report
      2007 Annual Research Report
  • [Presentation] Direct Diaryl Iodonium Salt Synthesis in Fluoro Alcohol Media2007

    • Author(s)
      土肥寿文 他
    • Organizer
      Green Sustainable Biological and Chemical Processes
    • Place of Presentation
      大阪
    • Year and Date
      2007-11-16
    • Related Report
      2007 Annual Research Report
  • [Presentation] Chemistry Using Hypervalent Iodine (III) Reagent: Oxidative Biaryl Coupling Reaction2007

    • Author(s)
      土肥寿文 他
    • Organizer
      Green Sustainable Biological and Chemical Processes
    • Place of Presentation
      大阪
    • Year and Date
      2007-11-16
    • Related Report
      2007 Annual Research Report
  • [Presentation] 水のみを副産物とする効果的ジアリールヨードニウム塩合成法の開発2007

    • Author(s)
      土肥寿文 他
    • Organizer
      第27回 有機合成若手セミナー
    • Place of Presentation
      京都
    • Year and Date
      2007-11-15
    • Related Report
      2007 Annual Research Report
  • [Presentation] 有機ヨウ素触媒を用いた酸化的スピロジェノン形成反応:溶媒効果と新触媒の開発2007

    • Author(s)
      土肥寿文 他
    • Organizer
      第33回 反応と合成の進歩シンポジウム
    • Place of Presentation
      長崎
    • Year and Date
      2007-11-06
    • Related Report
      2007 Annual Research Report
  • [Presentation] フルオロアルコール溶媒を活用する新規なジアリールヨードニウム塩合成法2007

    • Author(s)
      土肥寿文, 他
    • Organizer
      第57回日本薬学会近畿支部大会、総会
    • Place of Presentation
      大阪
    • Year and Date
      2007-10-27
    • Related Report
      2007 Annual Research Report
  • [Presentation] 有機ヨウ素触媒を用いるフェノール誘導体の酸化的スピロラクタム形成反応2007

    • Author(s)
      土肥寿文 他
    • Organizer
      日本プロセス化学会 サマーシンポジウム
    • Place of Presentation
      東京
    • Year and Date
      2007-08-02
    • Related Report
      2007 Annual Research Report
  • [Presentation] Catalytic Utilization of Hypervalent Iodiae (III) Reagents: Spirodienone Forming Reaction in Fluoroalcohol Medium2007

    • Author(s)
      土肥寿文 他
    • Organizer
      21st International Congress for Heterocyclic Chemistry
    • Place of Presentation
      オーストラリア、シドニー
    • Year and Date
      2007-07-17
    • Related Report
      2007 Annual Research Report
  • [Presentation] On the Development of Recyclable Hypervalent Iodine (III) Reagents Based on the Tetrahedral Structures2007

    • Author(s)
      土肥寿文, 他
    • Organizer
      21st International Congress for Heterocyclic Cheinistry
    • Place of Presentation
      オーストラリア、シドニー
    • Year and Date
      2007-07-17
    • Related Report
      2007 Annual Research Report
  • [Presentation] Oxidative Biaiyl Coupling of Electronic-Rich Aromatic and Heteroaromatic Compounds Using Hypervalent Iodiae (III) Reagents2007

    • Author(s)
      土肥寿文, 他
    • Organizer
      21st International Congress for Heterocyclic Cheinistry
    • Place of Presentation
      オーストラリア、シドニー
    • Year and Date
      2007-07-17
    • Related Report
      2007 Annual Research Report
  • [Patent(Industrial Property Rights)] ヨウ化物と、それを用いた酸化的不斉スピロ環形成方法2007

    • Inventor(s)
      土肥寿文, 他
    • Industrial Property Rights Holder
      大阪大学
    • Filing Date
      2007-12-20
    • Related Report
      2007 Annual Research Report

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Published: 2006-04-01   Modified: 2016-04-21  

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