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Development of novel metal-mediated reaction and their application to domino cyclization

Research Project

Project/Area Number 18390004
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionOsaka University

Principal Investigator

TANAKA Tetsuaki  Osaka University, 大学院・薬学研究科, 教授 (40116059)

Co-Investigator(Kenkyū-buntansha) YOSHIMITSU Takehiko  大阪大学, 大学院・薬学研究科, 准教授 (30301576)
KOJIMA Naoto  大阪大学, 大学院・薬学研究科, 助教 (90420413)
Project Period (FY) 2006 – 2008
Project Status Completed (Fiscal Year 2008)
Budget Amount *help
¥10,580,000 (Direct Cost: ¥9,200,000、Indirect Cost: ¥1,380,000)
Fiscal Year 2008: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
Fiscal Year 2007: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
Fiscal Year 2006: ¥4,600,000 (Direct Cost: ¥4,600,000)
Keywords有機化学 / 環境対応 / 生理活性 / パラジウム触媒 / 環境調和 / タンデム反応 / ブロモアレン / アリルジカチオン / アリールラジカル / スピロ環形成反応 / ラジカル環化 / π-アリルパラジウム錯体 / 不斉転位反応 / 1,4-不斉化合物
Research Abstract

遷移金属やランタノイド金属の化学は新反応の宝庫として近年特に注目を集めている研究領域である. これらの金属は, 典型金属には見られない特異な化学的性質を持ち,従来の手法では成し得なかった新規化学変換法や合成困難な物質の効率的かつ簡便な合成を次々に可能にしている. また, 環境調和型の合成化学が求められる今日, 触媒的な連続反応を開発することは極めて重要である. このような観点から, 報告者らは, 金属錯体の潜在特性を駆使した新規反応の開発に取り組み, 平成18~20年度に以下に示す新規反応の開発に成功した. (1) アリールラジカルを用いる新規スピロ環形成反応, (2) アレンの連続環化反応による複素環の新規合成法, (3) エンアレン類の[2+2]熱環化反応による複素環の新規合成法, (4) 求核部位を有するアレニルブロモアルケンの一挙環化反応, (5) プロパルギルブロミドを用いるドミノ型二環性骨格構築法, (6) オキシムエーテルに対するHeck 型反応, (7) パラジウム触媒を用いた芳香環C-H活性化を含む連続的閉環反応による多環式複素環の一挙合成, (8) パラジウム触媒を用いた不斉転位反応.

Report

(4 results)
  • 2008 Annual Research Report   Final Research Report ( PDF )
  • 2007 Annual Research Report
  • 2006 Annual Research Report
  • Research Products

    (46 results)

All 2008 2007 2006 Other

All Journal Article (18 results) (of which Peer Reviewed: 14 results) Presentation (26 results) Remarks (2 results)

  • [Journal Article] Samarium(II)-Mediated Spirocyclization byIntramolecular Aryl Radical Addition onto anAromatic Ring2008

    • Author(s)
      Hiroki Iwasaki, Toru Eguchi, Nozomi Tsutsui, Hiroaki Ohno, Tetsuaki Tanaka
    • Journal Title

      Journal of Organic Chemistry 73

      Pages: 7145-7152

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-catalysed biscyclisation ofallenic bromoalkenes through a zipper-modecascade2008

    • Author(s)
      Akinori Okano, Tsuyoshi Mizutani, ShinyaOishi, Tetsuaki Tanaka, Hiroaki Ohno, NobutakaFujii
    • Journal Title

      Chemical Communications

      Pages: 3534-3536

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Direct Construction of Bicyclic Heterocycles byPalladium-Catalyzed Domino Cyclization ofPropargyl Bromides2008

    • Author(s)
      Hiroaki Ohno, Akinori Okano, Shohei Kosaka, Koji Tsukamoto, Miyo Ohata, Kotaro Ishihara, Hatsuo Maeda, Tetsuaki Tanaka, Nobutaka Fujii
    • Journal Title

      Organic Letters 10

      Pages: 1171-1174

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Direct Construction of Bicyclic Heterocycles by Palladium-Catalyzed Domino Cyclization of Propargyl Bromides.2008

    • Author(s)
      Ohno, Hiroaki, Tetsuaki Tanaka, et al.
    • Journal Title

      Organic Letters 10

      Pages: 1171-1174

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-catalysed biscyclisation of allenic bromoalkenes through a zipper-mode cascade.2008

    • Author(s)
      Okano, Akinori, Tetsuaki Tanaka, et al.
    • Journal Title

      Chemical Communications

      Pages: 3534-3536

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Samarium(II)-Mediated Spirocyclization by Intramolecular Aryl Radical Addition onto an Aromatic Ring.2008

    • Author(s)
      Hiroki Iwasaki, Tetsuaki, Tanaka, et al.
    • Journal Title

      Journal of Organic Chemistry 73

      Pages: 7145-7152

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Heck-TypeCyclization of Oxime Ethers : StereoselectiveCarbon-Carbon Bond Formation with ArylHalides To Produce Heterocyclic Oximes2007

    • Author(s)
      Hiroaki Ohno, Akimasa Aso, Yoichi Kadoh,Nobutaka Fujii, Tetsuaki Tanaka
    • Journal Title

      Angewandte Chemie International Edition 46

      Pages: 6325-6328

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Zipper-Mode Double C-Hactivation : Palladium-Catalyzed DirectConstruction of Highly-Fused2007

    • Author(s)
      Hiroaki Ohno, Mutsumi Iuchi, Nobutaka Fujii, Tetsuaki Tanaka
    • Journal Title

      Heterocyclic Systems Organic Letters 9

      Pages: 4813-4815

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] A Highly Regio- and Stereoselective Formation of Bicyclo[4.2.0]oct-5-ene Derivatives through Thermal Intramolecular[2 + 2]Cycloaddition of Allenes2007

    • Author(s)
      Hiroaki Ohno, Tsuyoshi Mizutani, YoichiKadoh, Akimasa Aso, Kumiko Miyamura, Nobutaka Fujii, Tetsuaki Tanaka
    • Journal Title

      Journal of Organic Chemistry 72

      Pages: 4378-4389

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Bromoallenes as Allyl Dication Equivalents inthe Presence or Absence of Palladium(0) : DirectConstruction of Bicyclic Sulfamides ContainingFive- to Eight-membered Ring by Tandem Cyclization of Bromoallenes2007

    • Author(s)
      Hisao Hamaguchi, Shohei Kosaka, NobutakaFujii, Hiroaki Ohno, Tetsuaki Tanaka
    • Journal Title

      Chemistry of European Journal 13

      Pages: 1692-1708

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] A Highly Regio- and Stereoselective Formation of Bicyclo[4.2.0]oct-5-ene Derivatives through Thermal Intramolecular [2+2] Cycloaddition of Allenes2007

    • Author(s)
      Hiroaki Ohno, Tetsuaki Tanaka, et. al.
    • Journal Title

      Journal of Organic Chemistry 72

      Pages: 4378-4389

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Zipper-Mode Double C-H Activation: Palladium-Catalyzed Direct Construction of Highly-Fused Heterocyclic Systems2007

    • Author(s)
      Hiroaki Ohno, Tetsuaki Tanaka, et. al.
    • Journal Title

      Organic Letters 9

      Pages: 4813-4815

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Bromoallens as Allyl Dication Equivalents in the Presence or Absence of Palladium(O) : Direct Construction of Bicyclic Sulfamides Containing Five- to Eight-membered Rings by Tandem Cyclization of Bromoallenes2007

    • Author(s)
      Hisao Hamaguchi, Tetsuaki Tanaka et al.
    • Journal Title

      Chem. Eur. J. 13(6)

      Pages: 1692-1708

    • Related Report
      2006 Annual Research Report
  • [Journal Article] 芳香族CH 結合活性化を伴う連続反応の新展開2006

    • Author(s)
      大野浩章, 田中徹明
    • Journal Title

      化学 61

      Pages: 61-67

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Stereodivergent synthesis of 1, 4-bifunctionalcompounds by regio- and diastereoselectivePd-catalyzed allylic substitution reaction2006

    • Author(s)
      Naoyoshi Maezaki, Masahiro Yano, YukiHirose, Yoshikazu Itoh, Tetsuaki Tanaka
    • Journal Title

      Tetrahedron 62

      Pages: 10361-10378

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Stereodivergent synthesis of 1,4-bifunctional compounds by regio- and diastereoselective Pd-catalyzed allylic substitution reaction2006

    • Author(s)
      Naoyoshi Maezaki, Tetsuaki Tanaka et al.
    • Journal Title

      Tetrahedron 62(44)

      Pages: 10361-10378

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Construction of tricyclic enone, a common precursor for aphidicolane and stemodane B/C/D-ring system2006

    • Author(s)
      Tetsuaki Tanaka et al.
    • Journal Title

      Chem. Pharm. Bull. 54(8)

      Pages: 1138-1143

    • NAID

      110004847232

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Potassium Carbonate-Promoted Stereospecific 5-Endo-Trig Cyclization of Unactivated Allenes in the Absence of Any Transition Metals2006

    • Author(s)
      Hiroaki Ohno, Tetsuaki Tanaka et al.
    • Journal Title

      Org. Lett 8(5)

      Pages: 947-950

    • Related Report
      2006 Annual Research Report
  • [Presentation] パラジウム触媒を用いたブロモエンアレンの連続的閉環反応による多環式複素環の一挙構築2008

    • Author(s)
      岡野晃典, 大石真也, 大野浩章, 藤井信孝, 水谷剛, 田中徹明
    • Organizer
      第28回有機合成若手セミナー
    • Place of Presentation
      大阪
    • Year and Date
      2008-11-12
    • Related Report
      2008 Annual Research Report 2008 Final Research Report
  • [Presentation] パラジウム触媒を用いたブロモエンアレンの連続的閉環反応による多環式複素環の一挙構築2008

    • Author(s)
      岡野晃典, 大石真也, 大野浩章, 藤井信孝, 水谷剛, 田中徹明
    • Organizer
      第34回反応と合成の進歩シンポジウム
    • Place of Presentation
      京都
    • Related Report
      2008 Final Research Report
  • [Presentation] パラジウム触媒を用いたブロモエンアレンの連続環化反応による多環式複素環の一挙構築2008

    • Author(s)
      岡野晃典, 田中徹明, et al.
    • Organizer
      第34回反応と合成の進歩シンポジウム
    • Place of Presentation
      京都
    • Related Report
      2008 Annual Research Report
  • [Presentation] SmI_2-InducedRadical Spirocyclization Reaction BetweenAromatic Rings2007

    • Author(s)
      Hiroki Iwasaki, Toru Eguchi, Nozomi Tsutsui, Hiroaki Ohno, Tetsuaki Tanaka
    • Organizer
      Green Sustainable Biologicaland Chemical Process
    • Place of Presentation
      大阪
    • Year and Date
      2007-11-16
    • Related Report
      2008 Final Research Report
  • [Presentation] Direct Construction of BicyclicHeterocycles by Pd(0)- Catalyzed TandemCyclization of Propargylic Bromides2007

    • Author(s)
      Hiroaki Ohno, Shohei Kosaka, Akinori Okano, Kotaro Ishihara, Miyo Ohata, Nobutaka Fujii, Tetsuaki Tanaka
    • Organizer
      Green Sustainable Biological and Chemical Process
    • Place of Presentation
      大阪
    • Year and Date
      2007-11-16
    • Related Report
      2008 Final Research Report
  • [Presentation] Direct Construction of Bicyclic Heterocycles by Pd(0)- Catalyzed Tandem Cyclization of Propargylic Bromides2007

    • Author(s)
      Shohei Kosaka, Tetsuaki Tanaka, et. al.
    • Organizer
      Green Sustainable Biological and Chemical Process
    • Place of Presentation
      大阪府吹田市
    • Year and Date
      2007-11-16
    • Related Report
      2007 Annual Research Report
  • [Presentation] SmI_2-Induced Radical Spirocyclization Reaction Between Aromatic Rings2007

    • Author(s)
      Hiroki Iwasaki, Tetsuaki Tanaka, et. al.
    • Organizer
      Green Sustainable Biological and Chemical Process
    • Place of Presentation
      大阪府吹田市
    • Year and Date
      2007-11-16
    • Related Report
      2007 Annual Research Report
  • [Presentation] 連続結合形成反応による縮環型芳香族化合物の一挙合成法の開発2007

    • Author(s)
      大野浩章, 太田悠介, 大石真也, 藤井信孝, 井内睦美, 田中徹明
    • 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
      2007-11-05
    • Related Report
      2008 Final Research Report
  • [Presentation] パラジウム触媒を用いたプロパルギルブロミドの連続的閉環反応による二環性複素環の一挙構築2007

    • Author(s)
      岡野晃典, 大野浩章, 藤井信孝, 小坂昇平,大畑実代, 石原小太郎, 田中徹明, 塚本効司
    • 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
      2007-11-05
    • Related Report
      2008 Final Research Report
  • [Presentation] 連続結合形成反応による縮環型芳香族化合物の一挙合成法の開発2007

    • Author(s)
      大野浩章, 田中徹明.et. al.
    • Organizer
      第33回反応と合成の進歩シンポジウム
    • Place of Presentation
      長崎県長崎市
    • Year and Date
      2007-11-05
    • Related Report
      2007 Annual Research Report
  • [Presentation] ヨウ化サマリウムを用いた芳香環同士のラジカルカップリングによる新規スピロ環化反応の開発2007

    • Author(s)
      岩崎宏樹, 江口徹, 筒井望, 大野浩章, 田中徹明
    • Organizer
      第37回複素環化学討論会
    • Place of Presentation
      長野
    • Year and Date
      2007-10-18
    • Related Report
      2008 Final Research Report
  • [Presentation] ヨウ化サマリウムを用いた芳香環同士のラジカルカップリングによる新規スピロ環化反応の開発2007

    • Author(s)
      岩崎宏樹, 田中徹明.et. al.
    • Organizer
      第37回複素環化学討論会
    • Place of Presentation
      長野県長野市
    • Year and Date
      2007-10-18
    • Related Report
      2007 Annual Research Report
  • [Presentation] SmI_2-InducedRadical Spirocyclization Reaction BetweenAromatic Rings2007

    • Author(s)
      Hiroki Iwasaki, Toru Eguchi, Nozomi Tsutsui, Hiroaki Ohno, Tetsuaki Tanaka
    • Organizer
      21st International Congress forHeterocyclic Chemistry
    • Place of Presentation
      Sydney, Australia
    • Year and Date
      2007-07-16
    • Related Report
      2008 Final Research Report
  • [Presentation] Direct Construction ofBicyclic Heterocycles by Pd(0)- CatalyzedTandem Cyclization of Propargylic Bromides2007

    • Author(s)
      Shohei Kosaka, Akinori Okano, KotaroIshihara, Miyo Ohata, Nobutaka Fujii, HiroakiOhno, Tetsuaki Tanaka
    • Organizer
      21st International Congress for HeterocyclicChemistry
    • Place of Presentation
      Sydney, Australia
    • Year and Date
      2007-07-16
    • Related Report
      2008 Final Research Report
  • [Presentation] Direct Construction of Bicyclic Heterocycles by Pd(0)- Catalyzed Tandem Cyclization of Pronaraylic Bromides2007

    • Author(s)
      Shohei Kosaka, Tetsuaki Tanaka, et. al.
    • Organizer
      21st International Congress for Heterocyclic Chemistry
    • Place of Presentation
      Sydney, Australia
    • Year and Date
      2007-07-16
    • Related Report
      2007 Annual Research Report
  • [Presentation] SmI_2-Induced Radical Spirocyclization Reaction Between Aromatic Rings2007

    • Author(s)
      Hiroki Iwasaki, Tetsuaki Tanaka, et. al.
    • Organizer
      21st International Congress for Heterocyclic Chemistry
    • Place of Presentation
      Sydney, Australia
    • Year and Date
      2007-07-16
    • Related Report
      2007 Annual Research Report
  • [Presentation] Development of the NovelSpirocyclization Reaction Based on the RadicalReaction between Aromatic Rings using SmI22006

    • Author(s)
      岩崎宏樹, 江口徹, 筒井望, 大野浩章, 田中徹明
    • Organizer
      第26回有機合成若手セミナー
    • Place of Presentation
      大阪
    • Year and Date
      2006-12-14
    • Related Report
      2008 Final Research Report
  • [Presentation] オキシムエーテルを用いた炭素-窒素二重結合への新規Heck 型環化反応2006

    • Author(s)
      大野浩章, 麻生彬正, 加堂陽一, 田中徹明
    • Organizer
      第26回有機合成若手セミナー
    • Place of Presentation
      大阪
    • Year and Date
      2006-12-14
    • Related Report
      2008 Final Research Report
  • [Presentation] パラジウム触媒を用いたプロパルギルブロミドの連続的閉環反応による二環性複素環の一挙構築2006

    • Author(s)
      大野浩章, 小坂昇平, 岡野晃典, 大畑実代, 石原小太郎, 田中徹明
    • Organizer
      第56回日本薬学会近畿支部大会
    • Place of Presentation
      京都
    • Year and Date
      2006-10-28
    • Related Report
      2008 Final Research Report
  • [Presentation] パラジウム触媒を用いた芳香環C-H 活性化を含む連続的閉環反応による多環式複素環の一挙合成2006

    • Author(s)
      大野浩章, 井内睦実, 山本美緒, 田中徹明
    • Organizer
      第56回日本薬学会近畿支部大会
    • Place of Presentation
      京都
    • Year and Date
      2006-10-28
    • Related Report
      2008 Final Research Report
  • [Presentation] オキシムエーテルを用いた炭素-窒素二重結合への新規Heck 型環化反応2006

    • Author(s)
      大野浩章, 麻生彬正, 加堂陽一, 田中徹明
    • Organizer
      第56回日本薬学会近畿支部大会
    • Place of Presentation
      京都
    • Year and Date
      2006-10-28
    • Related Report
      2008 Final Research Report
  • [Presentation] ブロモアレンのタンデム閉環反応による二環性スルファミドの一挙構築2006

    • Author(s)
      大野浩章, 小坂昇平, 濱口壽雄, 田中徹明
    • Organizer
      第56回日本薬学会近畿支部大会
    • Place of Presentation
      京都
    • Year and Date
      2006-10-28
    • Related Report
      2008 Final Research Report
  • [Presentation] パラジウム触媒を用いた芳香環 C-H 活性化を含む連続的閉環反応による多環式複素環の一挙合成2006

    • Author(s)
      大野浩章, 井内睦実, 山本美緒, 田中徹明
    • Organizer
      第32回反応と合成の進歩シンポジウム
    • Place of Presentation
      広島
    • Related Report
      2008 Final Research Report
  • [Presentation] ブロモアレンのタンデム型閉環反応による二環性スルファミド類の一挙構築2006

    • Author(s)
      大野浩章, 小坂昇平, 濱口壽雄, 田中徹明
    • Organizer
      第32回反応と合成の進歩シンポジウム
    • Place of Presentation
      広島
    • Related Report
      2008 Final Research Report
  • [Presentation] Development of the Novel SpirocyclizationReaction Based on the Radical Reaction betweenAromatic Rings using SmI_22006

    • Author(s)
      Hiroki Iwasaki, Toru Eguchi, NozomiTsutsui, Hiroaki Ohno, Tetsuaki Tanaka
    • Organizer
      THE 3rdSEOUL-KYOTO-OSAKA JOINTSYMPOSIUM ON PHARMACEUTICALSCIENCES FOR YOUNG SCIENTISTS
    • Place of Presentation
      Korea, Seoul
    • Related Report
      2008 Final Research Report
  • [Presentation] Direct Constractionof Bicyclic Sulfamides Containing Five- toEight-membered Ring by Tandem Cyclization ofBromoallenes2006

    • Author(s)
      Hiroaki Ohno, Shohei Kosaka, HisaoHamaguchi, Tetsuaki Tanaka
    • Organizer
      THE 3rdSEOUL-KYOTO-OSAKA JOINTSYMPOSIUM ON PHARMACEUTICALSCIENCES FOR YOUNG SCIENTISTS
    • Place of Presentation
      Korea, Seoul
    • Related Report
      2008 Final Research Report
  • [Remarks] 第26回有機合成若手セミナー(2006年12月14日開催)での研究発表が評価され, 優秀研究発表賞を受賞した

    • Related Report
      2008 Final Research Report
  • [Remarks]

    • URL

      http://www.phs.osaka-u.ac.jp/homepage/b002/

    • Related Report
      2008 Annual Research Report

URL: 

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

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