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テトラチアフルバレンの集積型周辺修飾による拡張π共役系分子の創出

Publicly Offered Research

Project AreaOrganic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials
Project/Area Number 24106721
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionKyoto University

Principal Investigator

依光 英樹  京都大学, 理学(系)研究科(研究院), 准教授 (00372566)

Project Period (FY) 2012-04-01 – 2014-03-31
Project Status Completed (Fiscal Year 2013)
Budget Amount *help
¥6,760,000 (Direct Cost: ¥5,200,000、Indirect Cost: ¥1,560,000)
Fiscal Year 2013: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
Fiscal Year 2012: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
KeywordsTTF / ポルフィリン / アミノ化 / 縮環 / 時空間反応集積化 / パラジウム / π共役系 / テトラチアフルバレン / 光合成
Research Abstract

機能性π共役系母核周辺部に芳香環をはじめとする別のπ共役系ユニットを密集配置すれば、優れた機能・特性を有する斬新なπ共役系分子の創出に繋がる。本申請の研究ではテトラチアフルバレン(TTF)類の集積合成、具体的には同一時空間反応集積化に基づく複数の炭素―炭素結合の直接的一挙生成について検討した。今年度は特にジフェニルアミノ基がポルフィリンに三本の単結合で縮環した拡張ポルフィリンの高効率合成について集中的に研究を行った。
まず9-ブロモアントラセンやmeso-ブロモポルフィリンのようなかさ高いブロモアレーンをジアリールアミンでアミノ化する際の超高効率パラジウム触媒反応を開発した。具体的には、Organらが開発したPd-PEPPSI触媒を用いる反応系を改良し、目的に特化した反応条件を確立した。
効率よく合成できるようになったmeso-ジフェニルアミノポルフィリンを塩化鉄/DDQを用いて酸化すると、対応する縮環体が得られた。酸化反応を短時間で終了させると二つのフェニル基のうち一つだけが縮環した一重縮環体が、長時間行うと二つとも縮環した二重縮環体が生成した。X線結晶構造解析や各種分光学的測定を行ったところ、一重縮環体の方が二重縮環体よりもπ系が有効に共役していることが明らかとなった。
「周辺部窒素埋め込み型ポルフィリン」はその平面構造ゆえにポルフィリンよりも共役系が拡張しているだけでなく、窒素原子のおかげで電子的な柔軟性も獲得している。アザグラフェンの合成と物性探索において重要な知見となろう。

Current Status of Research Progress
Reason

25年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

25年度が最終年度であるため、記入しない。

Report

(2 results)
  • 2013 Annual Research Report
  • 2012 Annual Research Report
  • Research Products

    (22 results)

All 2014 2013 2012 Other

All Journal Article (12 results) (of which Peer Reviewed: 12 results) Presentation (9 results) (of which Invited: 9 results) Remarks (1 results)

  • [Journal Article] Synthesis of 7,8-Dehydropurpurin Dimers and Their Conversion to Conformationally Constrained β-to-β Vinylene-Bridged Porphyrin Dimers2014

    • Author(s)
      Norihito Fukui, Hideki Yorimitsu, Jong Min Lim, Dongho Kim, and Atsuhiro Osuka
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 53 Issue: 17 Pages: 4395-4398

    • DOI

      10.1002/anie.201400632

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Facile Preparation of β-Haloporphyrins as Useful Precursors of β-Substituted Porphyrins2014

    • Author(s)
      Keisuke Fujimoto, Hideki Yorimitsu, and Atsuhiro Osuka
    • Journal Title

      Org. Lett.

      Volume: 16 Issue: 3 Pages: 972-975

    • DOI

      10.1021/ol4037049

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Catalytic Activities of Porphyrin-Based PCP Pincer Complexes2014

    • Author(s)
      K. Fujimoto, T. Yoneda H. Yorimitsu, A. Osuka
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 53 Issue: 4 Pages: 1127-1130

    • DOI

      10.1002/anie.201308551

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Tetraarylation of 5,15-Dialkylporphyrins with Aryl Bromides2014

    • Author(s)
      Yutaro Yamamoto, Sumito Tokuji, Takayuki Tanaka, Hideki Yorimitsu, and Atsuhiro Osuka
    • Journal Title

      Heterocycles

      Volume: 88 Issue: 1 Pages: 223-231

    • DOI

      10.3987/com-13-s(s)5

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Amination of meso-Bromoporphyrins and 9-Haloanthracenes with Diarylamines Catalyzed by a Pd-PEPPSI Complex2013

    • Author(s)
      Yuko Suzuki, Norihito Fukui, Kei Murakami, Hideki Yorimitsu, and Atsuhiro Osuka
    • Journal Title

      Asian J. Org. Chem.

      Volume: 2 Issue: 12 Pages: 1066-1071

    • DOI

      10.1002/ajoc.201300162

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Oxidative Fusion Reactions of meso-(Diarylamino)porphyrins2013

    • Author(s)
      Norihito Fukui, Won-Young Cha, Sangsu Lee, Sumito Tokuji, Dongho Kim, Hideki Yorimitsu, and Atsuhiro Osuka
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 52 Issue: 37 Pages: 9728-9732

    • DOI

      10.1002/anie.201304794

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Demetalation of Metal Porphyrins via Magnesium Porphyrins by Reaction with Grignard Reagents2013

    • Author(s)
      村上慧、山元裕太郎、依光英樹、大須賀篤弘
    • Journal Title

      Chemistry- A European Journal

      Volume: 19 Issue: 28 Pages: 9123-9126

    • DOI

      10.1002/chem.201301146

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] TIPS-TTF as a Precursor of Low-Symmetry TTF DeriVatives: Steric Protection Strategy in the Regioselective C-H Modification of TTF2013

    • Author(s)
      上野遼太、藤野大士、依光英樹、大須賀篤弘
    • Journal Title

      Chemistry - A European Journal

      Volume: (印刷中) Issue: 22 Pages: 7156-7161

    • DOI

      10.1002/chem.201300623

    • Related Report
      2013 Annual Research Report 2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Extended Pummerer Reactions of Ketene Dithioacetal Monoxides with Alkynyl Sulfides and Ynamides with an Accompanying Oxygen Rearrangement2013

    • Author(s)
      村上慧、井本潤一、松原浩、吉田優、依光英樹、大嶌罵幸一郎
    • Journal Title

      Chemistry -A European Journal

      Volume: (In press) Issue: 18 Pages: 5625-5630

    • DOI

      10.1002/chem.201204072

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Direct Arylation of Porphyrin with π-Extended Aryl Bromides under Ligand-Free Fagnou-Hartwig Conditions2013

    • Author(s)
      Y. Yamamoto, S. Tokuji, T. Tanaka, H. Yorimitsu, A. Osuka
    • Journal Title

      Asian J. Org. Chem

      Volume: 2 Issue: 4 Pages: 320-324

    • DOI

      10.1002/ajoc.201200198

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Direct Arylation of meso-Formyl Porphyrin2013

    • Author(s)
      S. Tokuji, H. Awane, H. Yorimitsu, A. Osuka
    • Journal Title

      Chem. Eur. J.

      Volume: 19 Issue: 1 Pages: 64-68

    • DOI

      10.1002/chem.201203742

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Preferential Formation of Cyclic Trimers by Palladium-Catalyzed Oxidative Coupling Reactions of 2,18-Diethynylporphyrins2012

    • Author(s)
      S. Tokuji, H. Yorimitsu, A. Osuka
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 51 Issue: 49 Pages: 12357-12361

    • DOI

      10.1002/anie.201207763

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Presentation] ポルフィリンオリゴマーの時空間集積型一挙合成2014

    • Author(s)
      依光英樹
    • Organizer
      新学術領域研究「反応集積化の合成化学」平成25年度第2回成果報告会
    • Place of Presentation
      東京
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] 遷移金属触媒を駆使するπ電子系分子の合成2013

    • Author(s)
      依光英樹
    • Organizer
      第41回オルガノメタリックセミナー <錯体触媒化学のフロンティア>
    • Place of Presentation
      岡山
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Oxidative Fusions of meso-(Diarylamino)porphyrins2013

    • Author(s)
      Yorimitsu, H.; Fukui, N.; Tokuji, S.; Osuka, A.
    • Organizer
      15th International Symposium on Novel Aromatic Compounds
    • Place of Presentation
      台北
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] 硫黄の化学を温故知新2013

    • Author(s)
      依光英樹
    • Organizer
      新学術領域研究「反応集積化の合成化学」第2回若手合宿
    • Place of Presentation
      伊豆の国
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Synthesis of New Porphyrin-Based π Systems by Radical Reactions2013

    • Author(s)
      Yorimitsu, H.
    • Organizer
      6th Pacific Symposium on Radical Chemistry
    • Place of Presentation
      バンクーバー
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] パラジウム触媒を用いる新規ポルフィリンの高効率合成2013

    • Author(s)
      依光英樹
    • Organizer
      大阪市立大学理学研究科物質分子系専攻分子無機化学セミナー
    • Place of Presentation
      大阪
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Palladium-Catalyzed Direct Arylation of Functional Heteroaromatics2012

    • Author(s)
      Hideki Yorimitsu
    • Organizer
      3rd International Collaborative and Cooperative Chemistry Symposium
    • Place of Presentation
      Hangzhou, China
    • Year and Date
      2012-10-31
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Synthesis of Heteroaromatics by Utilizing Sulfur and Palladium2012

    • Author(s)
      Hideki Yorimitsu
    • Organizer
      Organic Reaction and Processes Gordon Research Conference
    • Place of Presentation
      Rhode Island, USA
    • Year and Date
      2012-07-15
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Catalytic Selective Direct Arylation of Porphyrin Periphery2012

    • Author(s)
      Hideki Yorimitsu and Atsuhiro Osuka
    • Organizer
      7th International Conference on Porphyrins and Phthalocyanines
    • Place of Presentation
      Jeju, Korea
    • Year and Date
      2012-07-01
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Remarks] 個人HP

    • URL

      http://kuchem.kyoto-u.ac.jp/shuyu/j/yorimitsu.html

    • Related Report
      2012 Annual Research Report

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Published: 2013-05-15   Modified: 2019-07-29  

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