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Transition Metal Catalyzed Synthesis of π-Conjugated Systems Having Main Group Elements

Research Project

Project/Area Number 19750074
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionTokyo University of Science (2008)
Kyoto University (2007)

Principal Investigator

MATSUDA Takanori  Tokyo University of Science, 理学部応用化学科, 講師 (80359778)

Project Period (FY) 2007 – 2008
Project Status Completed (Fiscal Year 2008)
Budget Amount *help
¥3,720,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥420,000)
Fiscal Year 2008: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2007: ¥1,900,000 (Direct Cost: ¥1,900,000)
Keywordsシロール / シラフルオレン / 閉環メタセシス / ヒドロシリル化 / ベンゾシロール / ベンゾフラン / フラン / 金 / ロジウム / ルテニウム / ジエン / エンイン / ジイン
Research Abstract

本年度は金触媒によるベンゾシロール骨格構築反応、ロジウム触媒によるベンゾフラン骨格構築反応を開発した。
1. Buchwald型ボスフィン配位子を持つカチオン性金触媒存在下、ジクロロメタン中室温下においてアリルジメチル(2-ペンチニルフェニル)シランを反応させたところ、分子内transアリルシリル化が進行し、3-アリル-1, 1-ジメチル-2-プロピルベンゾシロールを97%収率で与えた。アルキン末端置換基としてアルキル基、エステル基、アルキニル基、アリール基、ハロゲンが適用可能であり、対応するベンゾシロールを良好な収率で与えた。また、アリル基をメタリル基、クロチル基、シクロヘキセニル基などに変えても反応が進行した。同様の条件下、分子内transアリルゲルミル化によりベンゾゲルモール誘導体も得られた。
2. 2-フェニルエチニルフェノールを[RhCl(cod)]_2とrac-BINAPから調製した触媒存在下、トルエン中80℃で加熱したところ、分子内環化反応が進行し、2-フェニルベンゾフランが75%収率で得られた。10等量のアクリロニトリルの存在下、THF中80℃でこの反応を行うと、中間体のベンゾフラニルロジウム種の電子不足アルケンへの1, 4-付加が進行し、3-(2-フェニルベンゾフラン-3-イル)プロパンニトリルを75%収率で与えた。アクリロニトリルやメチルビニルケトンなどの電子不足アルケンも同様に反応し、対応する生成物を与えた。また、イソシアナートやホルムアルデヒドなどのカルボニル求電子剤も本反応に適用可能であった。分子内にあらかじめ求電子的な反応点を組み込んだ基質の反応では、連続的な酸素-炭素/炭素-炭素結合生成によって3環性、4環性のベンゾフラン誘導体が得られた。

Report

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

    (30 results)

All 2009 2008 2007

All Journal Article (14 results) (of which Peer Reviewed: 14 results) Presentation (15 results) Book (1 results)

  • [Journal Article] Palladium-Catalyzed Sequential Carbon?Carbon Bond Cleavage/Formation Producing Arylated Benzolactones2008

    • Author(s)
      Takanori Matsuda, Masanori Shigeno, and Masahiro Murakami
    • Journal Title

      Org. Lett 10

      Pages: 5219-5221

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Gold-catalysed intramolecular trans-allylsilylation of alkynes forming 3-allyl-1-silaindenes2008

    • Author(s)
      Takanori Matsuda, Sho Kadowaki, Yoshiyuki Yamaguchi, and Masahiro Murakami
    • Journal Title

      Chem. Commun

      Pages: 2744-2746

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Silole Skeletons via Metathesis Reactions2008

    • Author(s)
      Takanori Matsuda, Yoshiyuki Yamaguchi, and Masahiro Murakami
    • Journal Title

      Synlett

      Pages: 561-564

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Gold-Catalysed Intramolecular trans-Allylsilylation of Alkynes Forming 3-Allyl-1-silaindenes2008

    • Author(s)
      Takanori Matsuda
    • Journal Title

      Chemical Communications

      Pages: 2744-2746

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Sequential Carbon-Carbon Bond Cleavage/Formation Producing Arylated Benzolactones2008

    • Author(s)
      Takanori Matsuda
    • Journal Title

      Organic Letters 10

      Pages: 5219-5221

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Silole Skeletons via Metathesis Reactions2008

    • Author(s)
      Takanori Matsuda
    • Journal Title

      Synlett 4

      Pages: 561-564

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rhodium-Catalyzed Carbonylation of Spiropentanes2007

    • Author(s)
      Takanori Matsuda, Tomoya Tsuboi, and Masahiro Murakami
    • Journal Title

      J. Am. Chem. Soc 129

      Pages: 12596-12597

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Synthesis of 3,4-Dihydrocoumarins by Rhodium-Catalyzed Reaction of 3-(2-Hydroxyphenyl)cyclobutanones2007

    • Author(s)
      Takanori Matsuda, Masanori Shigeno, and Masahiro Murakami
    • Journal Title

      J. Am. Chem. Soc 129

      Pages: 12086-12087

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Ruthenium-Catalysed Double trans-Hydrosilylation of 1,4-Diarylbuta-1,3-diynes Leading to 2,5-Diarylsiloles2007

    • Author(s)
      Takanori Matsuda, Sho Kadowaki, and Masahiro Murakami
    • Journal Title

      Chem. Commun

      Pages: 2627-2629

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Rhodium-Catalyzed Reactions of Cyclobutanones with Alcohols and Amines Forming Esters and Amides2007

    • Author(s)
      Takanori Matsuda, Masanori Shigeno, Yohei Maruyama, and Masahiro Murakami
    • Journal Title

      Chem. Lett 36

      Pages: 744-745

    • NAID

      130004424769

    • Related Report
      2008 Final Research Report
    • Peer Reviewed
  • [Journal Article] Rhodium-Catalyzed Reactions of Cyclobutanones with Alcohols and Amines Forming Esters and Amides2007

    • Author(s)
      Takanori Matsuda
    • Journal Title

      Chemistry Letters 36・6

      Pages: 744-745

    • NAID

      130004424769

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ruthenium-Catalysed Double trans-Hydrosilylation of 1,4-Diarylbuta-1,3-diynes Leading to 2,5-Diarylsiloles2007

    • Author(s)
      Takanori Matsuda
    • Journal Title

      Chemical Communications 25

      Pages: 2627-2629

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Synthesis of 3,4-Dihydrocoumarins by Rhodium-Catalyzed Reaction of 3-(2-Hydroxyphenyl) cyclobutanones2007

    • Author(s)
      Takanori Matsuda
    • Journal Title

      Journal of the American Chemical Society 129・40

      Pages: 12086-12087

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rhodium-Catalyzed Carbonylation of Spiropentanes2007

    • Author(s)
      Takanori Matsuda
    • Journal Title

      Journal of the American Chemical Society 129・42

      Pages: 12596-12597

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Presentation] 金触媒によるアリールボロン酸のホモカップリング反応2009

    • Author(s)
      松田学則、浅井太郎
    • Organizer
      日本化学会第89春季年会
    • Place of Presentation
      日本大学理工学部船橋キャンパス
    • Year and Date
      2009-03-29
    • Related Report
      2008 Final Research Report
  • [Presentation] ロジウム触媒によるo-アルキニルフェノールの環化反応2009

    • Author(s)
      松田学則、藤崎陽介、坪井智也、村上正浩
    • Organizer
      日本化学会第89春季年会
    • Place of Presentation
      日本大学理工学部船橋キャンパス
    • Year and Date
      2009-03-28
    • Related Report
      2008 Final Research Report
  • [Presentation] Asymmetric Construction of Quaternary Carbon Centers by Rhodium-Catalyzed Enantioselective C?C Bond Cleavage2008

    • Author(s)
      Takanori Matsuda, Masanori Shigeno, Masaomi Makino, and Masahiro Murakami
    • Organizer
      5th Symposium on Chemical Approaches to Chirality
    • Place of Presentation
      Tokyo, Japan
    • Year and Date
      2008-12-01
    • Related Report
      2008 Final Research Report
  • [Presentation] ロジウム触媒による炭素?炭素結合切断反応の合成化学的利用2008

    • Author(s)
      松田学則
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学池袋キャンパス
    • Year and Date
      2008-03-27
    • Related Report
      2008 Final Research Report
  • [Presentation] パラジウム触媒によるシクロブタノンの炭素?炭素結合切断を経由するラクトン合成2008

    • Author(s)
      重野真徳、松田学則、村上正浩
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学池袋キャンパスおよび立教池袋中学校・高等学校
    • Year and Date
      2008-03-27
    • Related Report
      2008 Final Research Report
  • [Presentation] アルキンの分子内アリールシリル化によるシロール誘導体の合成2008

    • Author(s)
      山口善之、松田学則、村上正浩
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学池袋キャンパスおよび立教池袋中学校・高等学校
    • Year and Date
      2008-03-26
    • Related Report
      2008 Final Research Report
  • [Presentation] 遷移金属触媒によるジインの環化異性化反応2008

    • Author(s)
      呉屋剛、松田学則、村上正浩
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学池袋キャンパスおよび立教池袋中学校・高等学校
    • Year and Date
      2008-03-26
    • Related Report
      2008 Final Research Report
  • [Presentation] Rhodium-Catalyzed Asymmetric Synthesis of Lactones by Enantioselective C?C Bond Cleavage of Cyclobutanones2008

    • Author(s)
      Masanori Shigeno, Takanori Matsuda, and Masahiro Murakami
    • Organizer
      The 9th Youngnam?Kinki Joint Symposium on Organometallic Chemistry
    • Place of Presentation
      Kyoto, Japan
    • Year and Date
      2008-01-25
    • Related Report
      2008 Final Research Report
  • [Presentation] Synthesis of Siloles by Ruthenium-Catalyzed Double trans-Hydrosilylation of 1,3-Diynes2007

    • Author(s)
      Takanori Matsuda, Sho Kadowaki, Yoshiyuki Yamaguchi, and Masahiro Murakami
    • Place of Presentation
      Miyagi, Japan
    • Year and Date
      2007-11-02
    • Related Report
      2008 Final Research Report
  • [Presentation] ロジウム触媒による3-(2-ヒドロキシフェニル)シクロブタノンからの3,4-ジヒドロクマリンの不斉合成2007

    • Author(s)
      重野真徳、松田学則、村上正浩
    • Organizer
      第54回有機金属化学討論会
    • Place of Presentation
      広島大学東広島キャンパス
    • Year and Date
      2007-10-27
    • Related Report
      2008 Final Research Report
  • [Presentation] Asymmetric Synthesis of 3,4-Dihydrocoumarins by the Rhodium-Catalyzed Reaction of 3-(2-Hydroxyphenyl) cyclobutanones2007

    • Author(s)
      Masanori Shigeno
    • Organizer
      第54回有機金属討論会
    • Place of Presentation
      広島大学
    • Year and Date
      2007-10-27
    • Related Report
      2007 Annual Research Report
  • [Presentation] Rhodium-Catalyzed Asymmetric Synthesis of Lactones by Intramolecular Addition/Ring-Opening of Phenols to Cyclobutanones2007

    • Author(s)
      Masanori Shigeno, Takanori Matsuda, Masahiro Murakami
    • Organizer
      The Fourth International Symposium on Integrated Synthesis
    • Place of Presentation
      Shiga, Japan
    • Year and Date
      2007-09-23
    • Related Report
      2008 Final Research Report
  • [Presentation] 閉環メタセシス反応によるシロール骨格の合成2007

    • Author(s)
      山口善之、松田学則、村上正浩
    • Organizer
      第24回有機合成化学セミナー
    • Place of Presentation
      淡路夢舞台国際会議場
    • Year and Date
      2007-09-12
    • Related Report
      2008 Final Research Report
  • [Presentation] Synthesis of (±)-β-Cuparenone via Rhodium-Catalyzed Carbonylation of Spiropentane2007

    • Author(s)
      Takanori Matsuda, Tomoya Tsuboi, and Masahiro Murakami
    • Organizer
      14th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis(OMCOS14)
    • Place of Presentation
      Nara, Japan
    • Year and Date
      2007-08-03
    • Related Report
      2008 Final Research Report
  • [Presentation] Synthesis of Sesquiterpenes via Rhodium-Catalyzed Carbon?Carbon Bond Cleavage2007

    • Author(s)
      Takanori Matsuda, Masanori Shigeno, Tomoya Tsuboi, Masaomi Makino, and Masahiro Murakami
    • Organizer
      International Conference on Asymmetric Organocatalysis
    • Place of Presentation
      Shiga,Japan
    • Year and Date
      2007-05-29
    • Related Report
      2008 Final Research Report
  • [Book] Mingos, D. M. P., Crabtree, R. H., Ojima, I., Eds.; Elsevier : Oxford2007

    • Author(s)
      Michinori Suginome, Takanori Matsuda, Toshimichi Ohmura, Atsushi Seki, and Masahiro Murakami
    • Related Report
      2008 Final Research Report

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Published: 2007-04-01   Modified: 2016-04-21  

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