巨大環状ポリアレーンおよび巨大環状ポリヘテロアレーンの反応集積化による合成

• Project Area: Organic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials
• Project/Area Number: 22106539
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Tokyo Metropolitan University
• Principal Investigator: 伊與田 正彦 首都大学東京, 大学院・理工学研究科, 特任教授 (50115995)
• Project Period (FY): 2010 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000); Fiscal Year 2011: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2010: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
• Keywords: 選択的合成・反応 / 構造有機化学 / 有機巨大分子 / Lipshutz cuprate / 電子移動酸化 / ナノファイバー / ノナフェニレン / トリフェニレン三量体 / ミクロボール

Research Abstract

本研究は、申請者がこれまでに展開してきた研究を基礎とし、申請者の開発した反応の中で特に同一時空間反応集積化および時間的反応集積化を用いた合成反応に着目してその反応を改良し、巨大環状ポリアレーンおよび巨大環状ヘテロポリアレーンを高効率的に合成することを目的としている。このような研究の目的を実現するために、平成23年度においも平成22年度と同様にLipshutz cuprateの電子移動酸化および環状反応を用いて比較的小さな鎖状オリゴアレーンおよび鎖状オリゴヘテロアレーンを同一時空間反応集積化または時間的反応集積化を用いて合成した。また、ベンザイン前駆体を中間体に経るテルフェニルの合成は、込み合った分子骨格を合成できるので、本研究でさらに多重置換体の合成に応用した。さらに、鎖状オリゴヘテロアレーンとしては、ジチエノフランおよびジチエノピロールの効率的合成を検討した。また、平成23年度には、Lipshutz cuprateの電子移動酸化を用いる巨大環状ポリアレーンおよび巨大環状ヘテロポリアレーンの合成も計画していたので、温和な反応と考えられるLipshutz cuprateの電子移動酸化条件で、新たに導入した官能基が反応を妨げるか否かを先ず調べ、目的とした巨大環状ポリアレーンおよび巨大環状ヘテロポリアレーンの合成に取り組んだ。その結果、幾つかの巨大環状分子が合成できたので、その構造・性質および機能の関係を調べた。特に、本研究では自己組織化によってナノ構造を形成する巨大環状分子を構築することが目的であるから、その特異な構造の解析と、機能材料としての有用性についても調べた。

Research Products

• [Journal Article] Probing Coherence in Synthetic Cyclic Light-Harvesting Pigments (2011)
  • Author(s): M.Iyoda
  • Journal Title: J.Am.Chem.Soc. Volume: 113 Issue: 13 Pages: 4819-4828
  • DOI: 10.1021/ja108359w
  • Peer Reviewed
• [Journal Article] Nano-Sized to Giant Conjugated Macrocycles : New Concepts and Versatile Applications (2011)
  • Author(s): M.Iyoda
  • Journal Title: Angew.Chem.Int.Ed. Volume: 50 Pages: 10522-10553
  • Peer Reviewed
• [Journal Article] Synthesis and Nanostructures of Cyclic Triphenylene Trimers Having Long Alkyl and Aikoxy Side Chains (2011)
  • Author(s): M.Iyoda
  • Journal Title: Chem.Asian J. Volume: 6 Pages: 2940-2945
  • Peer Reviewed
• [Journal Article] Structural, Optical, and Electronic Properties of a Series of 3,4-Propylenedioxythiophene Oligomers in Neutral and Various Oxidation States (2011)
  • Author(s): M.Iyoda
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Issue: 29 Pages: 11339-11350
  • DOI: 10.1021/ja2035442
  • Peer Reviewed
• [Journal Article] Cyclic Tetrathiophenes Planarized by Silicon and Sulfur Bridges Bearing Antiaromatic Cyclooctatetraene Core : Syntheses, Structures, and Properties (2010)
  • Author(s): 伊與田正彦
  • Journal Title: J.Am.Chem.Soc. Volume: 132 Pages: 1066-1074
  • Peer Reviewed
• [Journal Article] Fully Conjugated Macrocycles Composed of Thiophenes, Acetylenes, and Ethylenes (2010)
  • Author(s): 伊與田正彦
  • Journal Title: Pure Appl.Chem. Volume: 82 Pages: 831-841
  • Peer Reviewed
• [Journal Article] Conducting supramolecular nanofibers and nanorods (2010)
  • Author(s): 伊與田正彦
  • Journal Title: Chem.Soc.Rev. Volume: 39 Pages: 2420-2427
  • Peer Reviewed
• [Journal Article] Synthesis and electrical conductivity of perchlorate-doped TTF diamide nanofibers (2010)
  • Author(s): 伊與田正彦
  • Journal Title: J.Mater.Chem. Volume: 20 Pages: 10817-10823
  • Peer Reviewed
• [Journal Article] Biradical Character of Linear π-Conjugated Oligomer Dications Composed of Thiophene, Pyrrole and Methylthio End-Capping Units (2010)
  • Author(s): 伊與田正彦
  • Journal Title: Org.Lett. Volume: 12 Pages: 5374-5377
  • Peer Reviewed
• [Journal Article] Shape-controllable gold nanocrystallization using an amphiphilic polythiophene (2010)
  • Author(s): 伊與田正彦
  • Journal Title: Chem.Commun. Volume: 46 Pages: 8603-8605
  • Peer Reviewed
• [Journal Article] Star-Shaped Oligothiophenes with Unique Photophysical Properties and Nanostructures (2010)
  • Author(s): 伊與田正彦
  • Journal Title: Chem.Eur.J. Volume: 16 Pages: 12108-12113
  • Peer Reviewed
• [Journal Article] An Efficient Synthesis of Chiral Isoquinuclidines by Diels-Alder Reaction Using Lewis Acid Catalyst (2010)
  • Author(s): 伊與田正彦
  • Journal Title: Tetrahedron Volume: 66 Pages: 7618-7624
  • NAID: 120003339540
  • Peer Reviewed
• [Journal Article] Synthesis and Properties of Octithiophene Dication Sterically Segregated by Annelation with Bicyclo[2.2.2]octene Units (2010)
  • Author(s): 伊與田正彦
  • Journal Title: Materials Volume: 3 Pages: 2037-2052
  • Peer Reviewed
• [Journal Article] Structural, electronic and magnetic properties of Cu(II) complexes of 2-substituted tropones bearing ferrocenyl group at 5-position (2010)
  • Author(s): 伊與田正彦
  • Journal Title: Dalton Trans. Volume: 39 Pages: 2420-2427
  • Peer Reviewed
• [Journal Article] Synthesis and p-Amphoteric Properties of Tris(tetrathiafulvaneno)hexadehydro-[12]annulene (2010)
  • Author(s): 伊與田正彦
  • Journal Title: Heterocycles Volume: 80 Pages: 909-915
  • Peer Reviewed
• [Journal Article] Synthesis of bitetrathiafulvalenes with FeCl_3-mediated homo-coupling of tetrathiafulvalenyl-magnesium chloride and molecular fiber formation form tetrakis(dodecylthio)tetrathiafulvalene (2010)
  • Author(s): 伊與田正彦
  • Journal Title: Tetrahedron Lett. Volume: 51 Pages: 679-682
  • Peer Reviewed
• [Presentation] Conducting Supramolecular Nanofibers and Nanorods (2011)
  • Author(s): M.Iyoda
  • Organizer: The International Symposium on Carbon Electronics (ISCE) & The STINT Summer School 2011
  • Place of Presentation: Seoul, Korea
• [Presentation] Nano-Sized to Giant Conjugated Macrocycles : Synthesis and Versatile Applications (2011)
  • Author(s): M.Iyoda
  • Organizer: The Seventh International Symposium on Integrated Synthesis (ISIS-7)
  • Place of Presentation: Kobe, Japan
• [Presentation] Self-Organization of Nano-Sized to Giant Conjugated Macrocycles : Synthesis and Functional Properties (2011)
  • Author(s): M.Iyoda
  • Organizer: BIT's 1st Annual World Congress on Nano-S&T (Nano-S&T 2011)
  • Place of Presentation: Dalian, China
• [Presentation] Self-organization of fully conjugated macrocycles : synthesis and functional properties (2010)
  • Author(s): 伊與田正彦
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 2010-12-19
• [Presentation] Conducting Supramolecular Nanofibers and Nanorods (2010)
  • Author(s): 伊與田正彦
  • Organizer: The 11th Eurasia Conference
  • Place of Presentation: The dead sea, Jordan
  • Year and Date: 2010-10-11
• [Book] Conjugated Molecular Belts Based on 3-D Benzannulene Systems (2011)
  • Author(s): M.Iyoda
  • Total Pages: 32
  • Publisher: Wiley-VCH
• [Book] 可溶性置換基をもつ3,4-ジオキシチオフェンオリゴマーの合成と基礎物性 (2011)
  • Author(s): 伊與田正彦
  • Total Pages: 7
  • Publisher: サイエンス&テクノロジー
• [Book] Fully Conjugated Nano-Sized Macrocycles : Syntheses and Versatile Properties (2010)
  • Author(s): 伊與田正彦
  • Total Pages: 30
  • Publisher: Wiley-VCH
• [Remarks]
  • URL: http://www.comp.tmu.ac.jp/iyoda/
• [Remarks]
  • URL: http://www.comp.tmu.ac.jp/iyoda/