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Regiocontrol of benzyne reaction by specific character of boryl group

Research Project

Project/Area Number 16K18843
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Chemical pharmacy
Research InstitutionKobe Pharmaceutical University

Principal Investigator

Takagi Akira  神戸薬科大学, 薬学部, 助教 (00758980)

Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2017: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2016: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywordsベンザイン / ホウ素 / 位置選択性 / 配位効果 / ボリル基 / 計算化学 / ジアミノナフタレン / ピナコール / 求核付加
Outline of Final Research Achievements

This research is controlling the regioselectivities of borylbenzynes. I tried to study regioselectivity of the reaction of borylbenzyne which containing various protective groups. Regioselectivities of reaction of borylbenynes were controlled by flexibility of the C-B bond or coordination of solvent. I also tried to discover the mechanism of regioselectivity of the reaction by calculation. These results were showed that the reaction of borylbenzyne provided both regioisomers and gave various multi-functionalized and multi-substituted aromatic compounds.

Academic Significance and Societal Importance of the Research Achievements

ベンザイン反応は反応性の高さから、多様な多置換芳香族化合物を合成できる有用な反応であるが、その反応性の高さ故に反応位置選択性の制御が困難であるという問題点があった。ボリルベンザインを用いた反応位置制御法は選択性制御の問題を解決する手法の一手となったが、片方の位置異性体が得られるのみであった。本研究成果によって、従来得られる異性体とは逆の異性体も自在に合成できる可能性を見出すことができたため、多様な多置換芳香族化合物を選択的に合成するための手法とすることができた。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (13 results)

All 2018 2017 2016

All Journal Article (3 results) (of which Peer Reviewed: 3 results,  Open Access: 1 results,  Acknowledgement Compliant: 1 results) Presentation (10 results) (of which Int'l Joint Research: 2 results)

  • [Journal Article] Synthesis of Optically Active 2,3-Disubstituted Indoline ?Derivatives through Cycloaddition Reactions between Benzynes and α,β-Unsaturated γ-Aminobutyronitriles2018

    • Author(s)
      Ikawa Takashi、Akai Shuji、Sumii Yuta、Masuda Shigeaki、Wang Ding、Emi Yuto、Takagi Akira
    • Journal Title

      Synlett

      Volume: 29 Issue: 04 Pages: 530-536

    • DOI

      10.1055/s-0036-1591722

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 3-(Triflyloxy)benzynes Enable the Regiocontrolled Cycloaddition of Cyclic Ureas to Synthesize 1,4-Benzodiazepine Derivatives2018

    • Author(s)
      Ikawa Takashi、Akai Shuji、Kaneko Hideki、Yamamoto Yuta、Arulmozhiraja Sundaram、Tokiwa Hiroaki
    • Journal Title

      Synlett

      Volume: 29 Issue: 07 Pages: 943-948

    • DOI

      10.1055/s-0036-1591924

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] 1,3- and 1,4-Benzdiyne Equivalents for Regioselective Synthesis of Polycyclic Heterocycles2016

    • Author(s)
      Ikawa, T.; Masuda, S.; Takagi, A.; Akai, S.
    • Journal Title

      Chemical Science

      Volume: 7 Issue: 8 Pages: 1-1

    • DOI

      10.1039/c6sc00798h

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Presentation] 市販のフェニルボロン酸誘導体からの新規ベンザイン発生法2018

    • Author(s)
      井川貴詞、Sun JingKai、高木 晃、赤井周司
    • Organizer
      第44回 反応と合成の進歩シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] One-pot Benzyne Generation from Commercially Available Phenylboronic Acids2018

    • Author(s)
      Takashi Ikawa、Sun JingKai、Akira Takagi、Shuji Akai
    • Organizer
      The 14th International Kyoto Conference on New Aspects of Organic Chemistry
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 反応性官能基を有するベンザインの効率的発生法の開発2017

    • Author(s)
      高木 晃
    • Organizer
      第67回日本薬学会近畿支部総会・大会
    • Related Report
      2017 Research-status Report
  • [Presentation] ベンザインの(2+2)付加環化ニ量化反応とその配向制御2017

    • Author(s)
      12.井川 貴詞,村上 智成,福元 豊,高木 晃,青山 浩,山本 雄大,常盤 広明,赤井 周司
    • Organizer
      第43回反応と合成の進歩シンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] ベンザインの[2+2]環化付加反応による新規らせん分子の合成2016

    • Author(s)
      井川貴詞、村上智成、福元 豊、高木 晃、青山 浩、山本雄大、常盤広明、赤井周司
    • Organizer
      第110回有機合成シンポジウム2016年【秋】
    • Place of Presentation
      早稲田大学国際会議場、東京
    • Year and Date
      2016-11-10
    • Related Report
      2016 Research-status Report
  • [Presentation] 2-ボリルフェニルノナフラートを前駆体とする温和な条件下でのベンザイン発生とベンゾ縮合複素環の合成2016

    • Author(s)
      高木 晃、井川貴詞、山本梨加、伊藤豊浩、赤井周司
    • Organizer
      第46回複素環化学討論会
    • Place of Presentation
      金沢歌劇座、石川
    • Year and Date
      2016-09-26
    • Related Report
      2016 Research-status Report
  • [Presentation] Copper-catalyzed regioselective three-component coupling reactions of borylbenzynes2016

    • Author(s)
      高木 晃、井川貴詞、清水和則、後藤雅彦、常盤広明、赤井周司
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      早稲田大学西早稲田キャンパス、東京
    • Year and Date
      2016-09-14
    • Related Report
      2016 Research-status Report
  • [Presentation] 1,3-Benzdiyne equivalent bearing traceless directing groups for regioselective synthesis of polycyclic angular heterocycles2016

    • Author(s)
      Takashi Ikawa, Shigeaki Masuda, Akira Takagi, Shuji Akai
    • Organizer
      7th Heron Island Conference on Reactive Intermediates and Unusual Molecules
    • Place of Presentation
      Heron Island, Australia
    • Year and Date
      2016-07-09
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] 2-ヒドロキシフェニルボロン酸を前駆体とする新規ベンザイン発生法の開発2016

    • Author(s)
      高木 晃、井川貴詞、山本梨加、赤井周司
    • Organizer
      第36回有機合成若手セミナー
    • Place of Presentation
      京都薬科大学、京都
    • Related Report
      2016 Research-status Report
  • [Presentation] 2-ヒドロキシフェニルボロン酸を前駆体とするベンザイン発生法の開発2016

    • Author(s)
      高木 晃、井川貴詞、赤井周司
    • Organizer
      第66回日本薬学会近畿支部総会・大会
    • Place of Presentation
      大阪薬科大学、大阪
    • Related Report
      2016 Research-status Report

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Published: 2016-04-21   Modified: 2020-03-30  

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