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Copper-catalyzed metalation reactions based on precise control of metal-Lewis acidity

Research Project

Project/Area Number 17K05864
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionHiroshima University

Principal Investigator

Yoshida Hiroto  広島大学, 工学研究科, 准教授 (40335708)

Project Period (FY) 2017-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2018: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2017: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywordsルイス酸性制御 / ボリル化 / スタニル化 / 銅触媒 / クロスカップリング / ルイス酸性抑制 / ホウ素化反応 / イリジウム触媒 / パラジウム触媒 / メタル化反応
Outline of Final Research Achievements

Copper-catalyzed borylative substitution reaction of allylic phosphates with diaminonaphtalene-substituted unsymmetrical diboron has been developed. A diaminonaphthalene-substituted boron moiety with diminished Lewis acidity has been found to be installed chemoselectively into the gamma position of the allylic phosphates, leading to the formation of various allylic boron compounds in high yields. In addition, we have succeeded in synthesizing an anthranilamide-substituted unsymmetrical diboron, which can be utilized for palladium-catalyzed borylative substitution of aryl halides. The resulting anthranilamide-sustituted aryl boron compounds have turned out to undergo direct Suzuki-Miyaura coupling without prior acidic deprotection. We have also achieved copper-catalyzed arylstannylation of arynes, which provides direct access to diverse biarylstannanes.

Academic Significance and Societal Importance of the Research Achievements

元来ルイス酸であるホウ素のルイス酸性を適切な置換様式で抑制し,それに付随するユニークな化学選択性を活かした触媒的ホウ素化反応群の開発に成功した.こうして直截的に得られるルイス酸性抑制型有機ホウ素化合物は,従来の有機ホウ素化合物に比べて空気や水に対し格段に安定となり,取り扱い・実用性の面で優位となる.一方でルイス酸性抑制は,有機ホウ素化合物のホウ素を起点とした変換の反応性を下げるためこれまで脱保護を要していたが,本研究ではルイス酸性抑制ホウ素をそのままクロスカップリングに利用する手法も確立した.今後の有用分子合成に広く利用可能な合成手法であるといえる.

Report

(4 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • 2017 Research-status Report
  • Research Products

    (52 results)

All 2020 2019 2018 2017 Other

All Journal Article (12 results) (of which Peer Reviewed: 12 results,  Open Access: 2 results) Presentation (30 results) (of which Int'l Joint Research: 8 results,  Invited: 4 results) Book (2 results) Remarks (8 results)

  • [Journal Article] Copper-Catalyzed B(dan)-Installing Allylic Borylation of Allylic Phosphates2019

    • Author(s)
      H. Yoshida, Y. Murashige, I. Osaka
    • Journal Title

      Adv. Synth. Catal.

      Volume: 361 Issue: 10 Pages: 2286-2290

    • DOI

      10.1002/adsc.201900342

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Anthranilamide (aam)-Substituted Arylboranes in Direct Carbon-Carbon Bond-Forming Reactions2019

    • Author(s)
      S. Kamio, I. Kageyuki, I. Osaka, H. Yoshida
    • Journal Title

      Chem. Commun.

      Volume: 55 Issue: 18 Pages: 2624-2627

    • DOI

      10.1039/c8cc10252j

    • Related Report
      2019 Annual Research Report 2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Anthranilamide-Substituted Borane [H-B(aam)]: Its Stability and Application to Iridium-Catalyzed Stereoselective Hydroboration of Alkynes2019

    • Author(s)
      H. Yoshida, M. Kimura, H. Tanaka, Y. Murashige, I. Kageyuki, I. Osaka
    • Journal Title

      Chem. Commun.

      Volume: 55 Issue: 38 Pages: 5420-5422

    • DOI

      10.1039/c9cc02002k

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Arylstannylation of Arynes in a Sequence2019

    • Author(s)
      H. Tanaka, H. Kuriki, T. Kubo, I. Osaka, H. Yoshida
    • Journal Title

      Chem. Commun.

      Volume: 55 Issue: 46 Pages: 6503-6506

    • DOI

      10.1039/c9cc02738f

    • NAID

      120006849362

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] One-pot Sequential Fluorostannylation-Arylstannylation of Arynes2019

    • Author(s)
      H. Tanaka, I. Osaka, H. Yoshida
    • Journal Title

      Chem. Lett.

      Volume: 48 Issue: 9 Pages: 1032-1034

    • DOI

      10.1246/cl.190385

    • NAID

      130007703025

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Borylation of Bromoaryl Triflates with Diborons: Chemoselective Replacement of an Ar-Br Bond2018

    • Author(s)
      Hiroto Yoshida, Shintaro Kamio, Itaru Osaka
    • Journal Title

      Chem. Lett.

      Volume: 47 Issue: 8 Pages: 957-959

    • DOI

      10.1246/cl.180385

    • NAID

      130007430981

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Preparation of (pin)B-B(dan)2018

    • Author(s)
      Hiroto Yoshida, Yuya Murashige, Itaru Osaka
    • Journal Title

      Org. Synth.

      Volume: 95 Pages: 218-230

    • DOI

      10.15227/orgsyn.095.0218

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Anthranilamide (aam)-Substituted Diboron: Palladium-Catalyzed Selective B(aam) Transfer2018

    • Author(s)
      Shintaro Kamio, Ikuo Kageyuki, Itaru Osaka, Sayaka Hatano, Manabu Abe, Hiroto Yoshida
    • Journal Title

      Chem. Commun.

      Volume: 54 Issue: 67 Pages: 9290-9293

    • DOI

      10.1039/c8cc05645e

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] B(MIDA)-Containing Diborons2017

    • Author(s)
      Hiroto Yoshida, Michinari Seki, Ikuo Kageyuki, Itaru Osaka, Sayaka Hatano, Manabu Abe
    • Journal Title

      ACS Omega

      Volume: 2 Issue: 9 Pages: 5911-5916

    • DOI

      10.1021/acsomega.7b01042

    • NAID

      120006811246

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Copper-Catalyzed Direct Borylation of Alkyl, Alkenyl and Aryl Halides with B(dan)2017

    • Author(s)
      Hiroto Yoshida, Yuki Takemoto, Shintaro Kamio, Itaru Osaka, Ken Takaki
    • Journal Title

      Org. Chem. Front.

      Volume: 4 Issue: 7 Pages: 1215-1219

    • DOI

      10.1039/c7qo00084g

    • NAID

      120006811244

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Borylstannylation of Alkynes with Tin Fluorides2017

    • Author(s)
      Hiroto Yoshida, Miki Kimura, Itaru Osaka, Ken Takaki
    • Journal Title

      Organometallics

      Volume: 36 Issue: 7 Pages: 1345-1351

    • DOI

      10.1021/acs.organomet.7b00058

    • NAID

      120006811243

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Ligand-Free Copper-Catalyzed Cyano- and Alkynylstannylation of Arynes2017

    • Author(s)
      Hiroto Yoshida, Teruhiko Kubo, Hitoshi Kuriki, Itaru Osaka, Ken Takaki, Yousuke Ooyama
    • Journal Title

      ChemistrySelect

      Volume: 2 Issue: 11 Pages: 3212-3215

    • DOI

      10.1002/slct.201700297

    • NAID

      120006811242

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Presentation] 塩基によるシリルスタナンを用いたハロゲン化アリールの置換型スタニル化反応2020

    • Author(s)
      平岡勇太,尾坂格,吉田拡人
    • Organizer
      日本化学会 第100春季年会 (2020)
    • Related Report
      2019 Annual Research Report
  • [Presentation] Synthesis of Ar-B(dan) by the Reaction of Aryl Grignard Reagents with H-B(dan)2020

    • Author(s)
      Jialun, Li, Michinari Seki, Itaru Osaka, Hiroto Yoshida
    • Organizer
      日本化学会 第100春季年会 (2020)
    • Related Report
      2019 Annual Research Report
  • [Presentation] 有機典型金属化合物の選択的合成法の開発とその応用2019

    • Author(s)
      吉田拡人
    • Organizer
      明治大学講演会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] 有機典型金属化合物の選択的合成法の開発とその応用2019

    • Author(s)
      吉田拡人
    • Organizer
      東京理科大学化学特別講義1
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Development of New Methods for Synthesizing Main Group Organometallic Compounds Including Boron and Tin2019

    • Author(s)
      Hiroto Yoshida
    • Organizer
      “Inviting Intelligence” Programme of the Beijing Univeristy of Chemical Technology
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Copper-Catalyzed Arylstannylation of Arynes in a Sequence2019

    • Author(s)
      Hideya Tanaka, Itaru Osaka, Hiroto Yoshida
    • Organizer
      The 16th Nano Bio Info Chemistry Symposium
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Copper-Catalyzed Arylstannylation of Arynes in Sequence2019

    • Author(s)
      Hideya Tanaka, Itaru Osaka, Hiroto Yoshida
    • Organizer
      20th IUPAC International Symposium on Organometallic Catalysis Directed Towards Organic Synthesis
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Copper-Catalyzed Arylstannylation of Arynes in a Sequence2019

    • Author(s)
      Hideya Tanaka, Itaru Osaka, Hiroto Yoshida
    • Organizer
      16th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Copper-Catalyzed Arylstannylation of Arynes in a Sequence2019

    • Author(s)
      Hideya Tanaka, Itaru Osaka, Hiroto Yoshida
    • Organizer
      National Central University-Hiroshima University Joint Symposium on Materials Chemistry and Physics 2019
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Direct Suzuki-Miyaura Coupling with Naphthalene-1,8-diaminato (dan)-Substituted Organoborons2019

    • Author(s)
      Hiroto Yoshida, Michinari Seki and Itaru Osaka
    • Organizer
      14th International Conference on Cutting-Edge Organic Chemistry in Asia
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] dan置換有機ホウ素化合物の直接クロスカップリング反応2019

    • Author(s)
      関道成,尾坂格,吉田拡人
    • Organizer
      第9回CSJ化学フェスタ2019
    • Related Report
      2019 Annual Research Report
  • [Presentation] 塩基によるシリルスタナンを用いたハロゲン化アリールのスタニル化反応2019

    • Author(s)
      平岡勇太,尾坂格,吉田拡人
    • Organizer
      第9回CSJ化学フェスタ2019
    • Related Report
      2019 Annual Research Report
  • [Presentation] ビアリール合成に向けたアラインの銅触媒アリールスタニル化の展開2019

    • Author(s)
      田中英也,尾坂格,吉田拡人
    • Organizer
      第124回触媒討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] dan置換有機ホウ素化合物の直接クロスカップリング反応2019

    • Author(s)
      関道成,尾坂格,吉田拡人
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] 銅触媒を用いたブロモアリールトリフラートの臭素部位選択的ホウ素化反応2019

    • Author(s)
      神尾慎太郎,尾坂格,吉田拡人
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] 銅触媒を用いたルイス酸性抑制非対称ジボロンによる末端アルキンのα選択的三成分連結ホウ素化反応2019

    • Author(s)
      対馬拓海,尾坂格,吉田拡人
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] 銅触媒を用いたアラインの連続的アリールスタニル化2019

    • Author(s)
      田中英也,尾坂格,吉田拡人
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Anthranilamide (aam)-Substituted Diboron: Palladium-Catalyzed Selective B(aam) Transfer2018

    • Author(s)
      Hiroto Yoshida
    • Organizer
      ICPAC Langkawi 2018
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Anthranilamide (aam)-Substituted Diboron: Pd-Catalyzed Selective B(aam) Transfer and Direct Cross-Coupling of Ar-B(aam) Therefrom2018

    • Author(s)
      Hiroto Yoshida, Shintaro Kamio, Itaru Osaka
    • Organizer
      IKCOC-14
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] アントラニルアミド置換ジボロン:パラジウム触 媒による選択的 B(aam)導入と直接クロスカップリング への展開2018

    • Author(s)
      神尾慎太郎,尾坂格,吉田拡人
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] 銅触媒を用いるアラインの1分子あるいは2分子選択的アリールスタニル化2018

    • Author(s)
      吉田拡人,田中英也,尾坂格
    • Organizer
      第122回触媒討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] アントラニルアミド(aam)置換非対称ジボロン:B(aam)導入反応および直接クロスカップリング2018

    • Author(s)
      神尾慎太郎,尾坂格,吉田拡人
    • Organizer
      第8回CSJ化学フェスタ
    • Related Report
      2018 Research-status Report
  • [Presentation] アリールスズのルイス酸性に基づいたアラインとの銅触媒連続的カップリング2018

    • Author(s)
      田中英也,尾坂格,吉田拡人
    • Organizer
      第8回CSJ化学フェスタ
    • Related Report
      2018 Research-status Report
  • [Presentation] アントラニルアミド置換ホウ素基の直接導入および直接クロスカップリング2018

    • Author(s)
      神尾慎太郎,尾坂格,吉田拡人
    • Organizer
      2018年日本化学会中国四国支部大会
    • Related Report
      2018 Research-status Report
  • [Presentation] アラインの銅触媒アリールスタニル化によるビアリール及びターアリールの直截合成2018

    • Author(s)
      田中英也,尾坂格,吉田拡人
    • Organizer
      2018年日本化学会中国四国支部大会
    • Related Report
      2018 Research-status Report
  • [Presentation] 銅触媒を用いたマスク型ジボロンによる置換型ホウ素化反応2017

    • Author(s)
      吉田拡人,村重有哉,尾坂格
    • Organizer
      第111回有機合成シンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] 銅触媒を用いたアラインのアリールスタニル化反応2017

    • Author(s)
      吉田拡人,田中英也,尾坂格
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] ジアミノナフタレン置換非対称ジボロンを用いた炭素求電子剤の銅触媒置換型ホウ素化反応2017

    • Author(s)
      吉田拡人,村重有哉,尾坂格
    • Organizer
      第120回触媒討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] アントラニルアミド置換非対称ジボロンを用いたハロゲン化アリールのパラジウム触媒置換型ホウ素化反応2017

    • Author(s)
      吉田拡人,神尾慎太郎,尾坂格
    • Organizer
      第120回触媒討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] アントラニルアミド置換非対称ジボロンを用いたアルキンの銅触媒位置選択的ヒドロホウ素化反応2017

    • Author(s)
      吉田拡人,対馬拓海,尾坂格
    • Organizer
      第120回触媒討論会
    • Related Report
      2017 Research-status Report
  • [Book] 高反応性のアラインを簡単につなぐ!2020

    • Author(s)
      田中英也,吉田拡人
    • Total Pages
      7
    • Publisher
      化学同人
    • Related Report
      2019 Annual Research Report
  • [Book] Diboron Compounds: Synthesis and Applications, in Science of Synthesis Reference Library: Advances in Organoboron Chemistry toward Organic Synthesis2020

    • Author(s)
      Hiroto Yoshida
    • Total Pages
      52
    • Publisher
      Thieme
    • ISBN
      9783132429758
    • Related Report
      2019 Annual Research Report
  • [Remarks] 広島大学大学院工学研究科応用化学専攻反応設計化学研究室ホームページ

    • URL

      https://home.hiroshima-u.ac.jp/~rdc/

    • Related Report
      2019 Annual Research Report
  • [Remarks] 広島大学ホームページ【研究成果】『化学(化学同人)』の最新号で紹介されました

    • URL

      https://www.hiroshima-u.ac.jp/news/55802

    • Related Report
      2019 Annual Research Report
  • [Remarks] アラインをパズルのピースのように繋げる!

    • URL

      https://www.chem-station.com/blog/2019/06/aryne.html

    • Related Report
      2019 Annual Research Report
  • [Remarks] 広島大学ホームページ【研究成果】『Chem-Station』で紹介されました

    • URL

      https://www.hiroshima-u.ac.jp/news/51693

    • Related Report
      2019 Annual Research Report
  • [Remarks] 広島大学ホームページプレスリリース

    • URL

      https://www.hiroshima-u.ac.jp/news/51349

    • Related Report
      2019 Annual Research Report
  • [Remarks] 第8回CSJ化学フェスタ2018における最優秀ポスター発表賞(CSJ化学フェスタ賞)受賞

    • URL

      https://www.hiroshima-u.ac.jp/news/48649

    • Related Report
      2018 Research-status Report
  • [Remarks] 所属研究室ホームページ

    • URL

      https://home.hiroshima-u.ac.jp/~rdc/

    • Related Report
      2018 Research-status Report
  • [Remarks] 広島大学大学院工学研究科応用化学専攻反応設計化学研究室

    • URL

      http://home.hiroshima-u.ac.jp/~rdc/

    • Related Report
      2017 Research-status Report

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Published: 2017-04-28   Modified: 2021-02-19  

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