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フロー系が可能にするプメラー型ビアリール構築による中分子合成

Publicly Offered Research

Project AreaMiddle molecular strategy: Creation of higher bio-functional molecules by integrated synthesis.
Project/Area Number 18H04409
Research Category

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

Allocation TypeSingle-year Grants
Research InstitutionKyoto University

Principal Investigator

依光 英樹  京都大学, 理学研究科, 教授 (00372566)

Project Period (FY) 2018-04-01 – 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: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Fiscal Year 2018: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Keywordsプメラー反応 / アニリン / 含窒素ヘテロ環 / ビアリール / マイクロフローリアクター / シグマトロピー転位 / Pummerer型反応 / ヘリセン
Outline of Annual Research Achievements

フローリアクターを駆使しつつ、主に以下の成果を得た。
1)アルケニルスルホキシドの拡張プメラー反応を利用したアゾール類の合成
KDMとニトリルをトリフルオロメタンスルホン酸無水物存在下反応させることによって、Additiveプメラー反応と環化を経てチアゾールが得られることを見いだした。トリフルオロメタンスルホン酸無水物によって活性化され生じたスルホニウムに対して、ニトリルがリッター型のadditiveプメラー反応を起こし、対応するニトリリウム中間体が生じる。続く環化、脱プロトン化、硫黄上の脱メチル化を経てチアゾールが生成したと考えられる。この反応は、リッター型のadditiveプメラー反応の初めての例となる。また、水共存下で同様の反応を行うと、ニトリリウムカチオンに水が付加し、続いて環化が起こることでオキサゾリン中間体が生じ、チオールの脱離を伴う芳香族化を経てオキサゾールが生じることも見つけた。
2)アニリン類を求核剤とするプメラー型反応
アリールスルホキシドとアニリンの混合物に対し、トリフルオロメタンスルホン酸無水物を作用させると対応するスルフィルイミンが生じた。ここにトリフルオロメタンスルホン酸をさらに加えたところ、高反応性のジカチオン性化学種が発生し、シグマトロピー転位によりo-アミノ-o-スルファニルビアリールが生成することを明らかにした。また、窒素上に電子求引性のスルホニル基を導入したスルホニルアニリンを用いた場合には、より反応性の低いトリフルオロ酢酸無水物で反応が進行することを明らかにした。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

Report

(2 results)
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • Research Products

    (46 results)

All 2020 2019 2018 Other

All Int'l Joint Research (3 results) Journal Article (27 results) (of which Int'l Joint Research: 5 results,  Peer Reviewed: 27 results,  Open Access: 4 results) Presentation (10 results) (of which Int'l Joint Research: 1 results,  Invited: 2 results) Remarks (5 results) Funded Workshop (1 results)

  • [Int'l Joint Research] デリー大学(インド)

    • Related Report
      2019 Annual Research Report
  • [Int'l Joint Research] カタロニア触媒化学研究所(スペイン)

    • Related Report
      2019 Annual Research Report
  • [Int'l Joint Research] Columbia University(米国)

    • Related Report
      2018 Annual Research Report
  • [Journal Article] Ni-Catalyzed Carboxylation of C(sp2)?S Bonds with CO2: Evidence for the Multifaceted Role of Zn2020

    • Author(s)
      Yanagi Tomoyuki、Somerville Rosie J.、Nogi Keisuke、Martin Ruben、Yorimitsu Hideki
    • Journal Title

      ACS Catalysis

      Volume: 10 Issue: 3 Pages: 2117-2123

    • DOI

      10.1021/acscatal.9b05141

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Tf2O-mediated Reaction of Alkenyl Sulfoxides with Unprotected Anilines in Flow Microreactors2020

    • Author(s)
      Baralle Alexandre、Inukai Tomoaki、Yanagi Tomoyuki、Nogi Keisuke、Osuka Atsuhiro、Nagaki Aiichiro、Yoshida Jun-ichi、Yorimitsu Hideki
    • Journal Title

      Chemistry Letters

      Volume: 49 Issue: 2 Pages: 160-163

    • DOI

      10.1246/cl.190831

    • NAID

      130007795212

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Reductive Difunctionalization of Aryl Alkenes with Sodium Metal and Reduction-Resistant Alkoxy-Substituted Electrophiles2020

    • Author(s)
      Fukazawa Mizuki、Takahashi Fumiya、Nogi Keisuke、Sasamori Takahiro、Yorimitsu Hideki
    • Journal Title

      Organic Letters

      Volume: 22 Issue: 6 Pages: 2303-2307

    • DOI

      10.1021/acs.orglett.0c00490

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Annulative Synthesis of Thiazoles and Oxazoles from Alkenyl Sulfoxides and Nitriles via Additive Pummerer Reaction2019

    • Author(s)
      Hori Mitsuki、Nogi Keisuke、Nagaki Aiichiro、Yorimitsu Hideki
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 8 Issue: 7 Pages: 1084-1087

    • DOI

      10.1002/ajoc.201900169

    • NAID

      120006709414

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Palladium-Catalyzed Amination of Aryl Sulfides and Sulfoxides with Azaarylamines of Poor Nucleophilicity2019

    • Author(s)
      Pratap Ramendra、Yorimitsu Hideki
    • Journal Title

      Synthesis

      Volume: 51 Issue: 13 Pages: 2705-2712

    • DOI

      10.1055/s-0037-1611732

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Palladium-Catalyzed Alkoxycarbonylation of Arylsulfoniums2019

    • Author(s)
      Minami Hiroko、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 8 Pages: 2518-2522

    • DOI

      10.1021/acs.orglett.9b00067

    • NAID

      120006621582

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Aromatic Metamorphosis of Indoles into 1,2-Benzazaborins2019

    • Author(s)
      Tsuchiya Shun、Saito Hayate、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 10 Pages: 3855-3860

    • DOI

      10.1021/acs.orglett.9b01353

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Diborative Reduction of Alkynes to 1,2-Diboryl-1,2-Dimetalloalkanes: Its Application for the Synthesis of Diverse 1,2-Bis(boronate)s2019

    • Author(s)
      Takahashi Fumiya、Nogi Keisuke、Sasamori Takahiro、Yorimitsu Hideki
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 12 Pages: 4739-4744

    • DOI

      10.1021/acs.orglett.9b01622

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper-Catalyzed Twofold Silylmetalation of Alkynes2019

    • Author(s)
      Yamagishi Hiroki、Shimokawa Jun、Yorimitsu Hideki
    • Journal Title

      Synlett

      Volume: 30 Issue: 13 Pages: 1551-1554

    • DOI

      10.1055/s-0037-1611869

    • NAID

      120006715508

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of N-Alkyl and N-H Carbazoles via SNAr‐based Aminations of Dibenzothiophene dioxides2019

    • Author(s)
      Kaga Atsushi、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Chemistry - A European Journal

      Volume: 25 Issue: 65 Pages: 14780-14784

    • DOI

      10.1002/chem.201903916

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Arylthiolation of Alkynes Enabled by Surmounting Competitive Dimerization of Alkynes2019

    • Author(s)
      Uno Daisuke、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 20 Pages: 8295-8299

    • DOI

      10.1021/acs.orglett.9b03056

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cross-Coupling of Aryl Trifluoromethyl Sulfones with Arylboronates by Cooperative Palladium/Rhodium Catalysis2019

    • Author(s)
      Fukuda Jun-ichi、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 22 Pages: 8987-8991

    • DOI

      10.1021/acs.orglett.9b03393

    • NAID

      120006800717

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Construction of Biaryls from Aryl Sulfoxides and Anilines by Means of a Sigmatropic Rearrangement2019

    • Author(s)
      Yanagi Tomoyuki、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Chemistry A European Journal

      Volume: 26 Issue: 4 Pages: 783-787

    • DOI

      10.1002/chem.201903570

    • NAID

      120006800745

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Sulfoxide-Directed Iterative Assembly into Oligoarenes2019

    • Author(s)
      Yanagi Tomoyuki、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Synlett

      Volume: 印刷中 Issue: 02 Pages: 153-157

    • DOI

      10.1055/s-0037-1611767

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Annulative Synthesis of Benzofurans from General Alkenyl Sulfoxides and Phenols via Pummerer/Sigmatropic Cascade2019

    • Author(s)
      Hori Mitsuki、Yanagi Tomoyuki、Murakami Kei、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 92 Issue: 2 Pages: 302-311

    • DOI

      10.1246/bcsj.20180321

    • NAID

      130007593735

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Photoredox-Catalyzed Alkenylation of Benzylsulfonium Salts2019

    • Author(s)
      Otsuka Shinya、Nogi Keisuke、Rovis Tomislav、Yorimitsu Hideki
    • Journal Title

      Chemistry - An Asian Journal

      Volume: 14 Issue: 4 Pages: 532-536

    • DOI

      10.1002/asia.201801732

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Palladium-Catalyzed Homo-Coupling of Heteroarylsulfoniums via Borylation/Suzuki-Miyaura Coupling Sequence2018

    • Author(s)
      Minami Hiroko、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      HETEROCYCLES

      Volume: 97 Issue: 2 Pages: 998-998

    • DOI

      10.3987/com-18-s(t)78

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium‐Catalyzed Insertion of Isocyanides into the C‐S Bonds of Heteroaryl Sulfides2018

    • Author(s)
      Otsuka Shinya、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Angewandte Chemie - International Edition

      Volume: 印刷中 Issue: 22 Pages: 6653-6657

    • DOI

      10.1002/anie.201802369

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Mizoroki-Heck-Type Alkenylation of Monoaryldialkylsulfoniums2018

    • Author(s)
      Uno Daisuke、Minami Hiroko、Otsuka Shinya、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Chemistry - An Asian Journal

      Volume: 13 Issue: 17 Pages: 2397-2400

    • DOI

      10.1002/asia.201800489

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] “Macroscopically Anisotropic Structures Produced by Lightinduced Solvothermal Assembly of Porphyrin Dimers”2018

    • Author(s)
      Y. Yamamoto, Y. Nishimura, S. Tokonami, N. Fukui, T. Tanaka, A. Osuka, H. Yorimitsu, and T. Iida
    • Journal Title

      Sci. Rep.

      Volume: 8 Issue: 1 Pages: 11108-11108

    • DOI

      10.1038/s41598-018-28311-2

    • NAID

      120006539601

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Copper-Catalyzed Ring-Opening Silylation of Benzofurans with Disilane2018

    • Author(s)
      Saito Hayate、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 57 Issue: 34 Pages: 11030-11034

    • DOI

      10.1002/anie.201806237

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of 4-aryl- and 4-acyl-1,3-dithiole-2-thiones via deprotonative zincation of 1,3-dithiole-2-thione2018

    • Author(s)
      Otsuka Shinya、Yorimitsu Hideki
    • Journal Title

      Heteroatom Chemistry

      Volume: 29 Issue: 3

    • DOI

      10.1002/hc.21432

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cobalt-Catalyzed Reduction of Aryl Sulfones to Arenes by Means of Alkylmagnesium Reagents2018

    • Author(s)
      Fukuda Jun-ichi、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 7 Issue: 10 Pages: 2049-2052

    • DOI

      10.1002/ajoc.201800473

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Sigmatropic Dearomatization/Defluorination Strategy for C-F Transformation: Synthesis of Fluorinated Benzofurans from Polyfluorophenols2018

    • Author(s)
      Okamoto Koichi、Hori Mitsuki、Yanagi Tomoyuki、Murakami Kei、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 57 Issue: 43 Pages: 14230-14234

    • DOI

      10.1002/anie.201809035

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Intramolecular Desulfitative Coupling: Nickel-Catalyzed Transformation of Diaryl Sulfones into Biaryls via Extrusion of SO22018

    • Author(s)
      Takahashi Fumiya、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Organic Letters

      Volume: 20 Issue: 20 Pages: 6601-6605

    • DOI

      10.1021/acs.orglett.8b02972

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] C-S Bond Activation2018

    • Author(s)
      Otsuka Shinya、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Topics in Current Chemistry

      Volume: 376 Issue: 2 Pages: 13-13

    • DOI

      10.1007/s41061-018-0190-7

    • NAID

      120006621579

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Recent development of ortho -C?H functionalization of aryl sulfoxides through [3,3] sigmatropic rearrangement2018

    • Author(s)
      Yanagi Tomoyuki、Nogi Keisuke、Yorimitsu Hideki
    • Journal Title

      Tetrahedron Letters

      Volume: 59 Issue: 31 Pages: 2951-2959

    • DOI

      10.1016/j.tetlet.2018.06.055

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Presentation] アリールスルホキシドとフェノールの脱水素カップリング反応に関する機構解析2020

    • Author(s)
      柳智征・野木馨介・依光英樹
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] [3,3] シグマトロピー転位を利用したケテンジチオアセタールモノオキシドとN-スルホニルアニリンからのインドール合成2020

    • Author(s)
      木下純・吉田陽・岡本浩一・柳智征・野木馨介・依光英樹
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ニッケル触媒によるアリールスルホニウム塩の還元的亜鉛化2020

    • Author(s)
      山田航大・柳智征・野木馨介・依光英樹
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 高エネルギースルホニウムカチオンが拓く有機合成2019

    • Author(s)
      依光英樹
    • Organizer
      第29回万有福岡シンポジウム
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Nickel-Catalyzed Carboxylation of Arylsulfoniums2019

    • Author(s)
      Tomoyuki Yanagi, Keisuke Nogi, Ruben Martin, and Hideki Yorimitsu
    • Organizer
      The 20th IUPAC Conference on Organometallic Chemistry Directed Towards Organic Synthesis
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] アリールスルホキシドとアニリン誘導体を用いた[3,3]シグマトロピー転位によるビアリール合成2019

    • Author(s)
      吉田陽、岡本浩一、柳智征、野木馨介、依光英樹
    • Organizer
      第39回有機合成若手セミナー
    • Related Report
      2019 Annual Research Report
  • [Presentation] アリールスルホキシドとアニリン誘導体を用いた[3,3]シグマトロピー転位によるビアリール合成2019

    • Author(s)
      吉田陽、岡本浩一、柳智征、野木馨介、依光英樹
    • Organizer
      第36回有機合成化学セミナー
    • Related Report
      2019 Annual Research Report
  • [Presentation] アリールスルホキシドとフェノールの脱水素カップリング反応に関する機構解析2019

    • Author(s)
      柳智征・野木馨介・依光英樹
    • Organizer
      第46回有機典型元素化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] アリールスルホキシドとアニリン誘導体を用いた[3,3]シグマトロピー転位によるビアリール合成2019

    • Author(s)
      吉田陽、岡本浩一、柳智征、野木馨介、依光英樹
    • Organizer
      第46回有機典型元素化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 高エネルギースルホニウムカチオンが拓く高難度分子変換2019

    • Author(s)
      依光英樹
    • Organizer
      日本化学会第99春季年会「特別企画」未来機能を生み出すp-ブロック統合化学
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Remarks] 研究室HP

    • URL

      http://kuchem.kyoto-u.ac.jp/orgchem/

    • Related Report
      2019 Annual Research Report 2018 Annual Research Report
  • [Remarks] 「驚きの有機化学反応を創り育てる」 京都大学理学研究科・理学部研究紹介インタビュー

    • URL

      http://www.sci.kyoto-u.ac.jp/ja/research/activities-ch/1910-hidekiyorimitsu.html

    • Related Report
      2019 Annual Research Report
  • [Remarks] 化学専攻 依光英樹教授が日本学術振興会賞を受賞

    • URL

      http://www.sci.kyoto-u.ac.jp/ja/news/detail_1557.html

    • Related Report
      2019 Annual Research Report
  • [Remarks] 化学専攻 依光英樹教授が日本学士院学術奨励賞を受賞

    • URL

      http://www.sci.kyoto-u.ac.jp/ja/news/detail_1575.html

    • Related Report
      2019 Annual Research Report
  • [Remarks] 依光英樹 理学研究科教授が第16回(令和元年度)日本学士院学術奨励賞を受賞

    • URL

      http://www.kyoto-u.ac.jp/ja/about/events_news/office/soumu/koho/news/2019/200114_1.html

    • Related Report
      2019 Annual Research Report
  • [Funded Workshop] International Symposium on Main Group Chemistry Directed towards Organic Synthesis2018

    • Related Report
      2018 Annual Research Report

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Published: 2018-04-23   Modified: 2021-01-27  

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