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Development of Integrated Synthetic Processes Based on Combined Experimental and Theoretical Studies

Research Project

Project/Area Number 16KT0051
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeMulti-year Fund
Section特設分野
Research Field Transition State Control
Research InstitutionNagoya University

Principal Investigator

Yamamoto Yoshihiko  名古屋大学, 創薬科学研究科, 教授 (60283412)

Project Period (FY) 2016-07-19 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥18,460,000 (Direct Cost: ¥14,200,000、Indirect Cost: ¥4,260,000)
Fiscal Year 2018: ¥5,330,000 (Direct Cost: ¥4,100,000、Indirect Cost: ¥1,230,000)
Fiscal Year 2017: ¥5,330,000 (Direct Cost: ¥4,100,000、Indirect Cost: ¥1,230,000)
Fiscal Year 2016: ¥7,800,000 (Direct Cost: ¥6,000,000、Indirect Cost: ¥1,800,000)
Keywords遷移金属触媒 / DFT計算 / 遷移状態 / 環化反応 / 生理活性化合物 / 複素環化合物 / 反応機構 / DFT分子軌道計算 / DFT計算 / ルテニウム触媒 / パラジウム触媒 / 銅触媒 / アルキン
Outline of Final Research Achievements

Novel Transition-metal-catalyzed annulation reactions have been developed in this study. Efficient constructions of cyclic molecular frameworks involving multiple bond formations were achieved using ruthenium, rhodium, and palladium complexes as the catalysts. Density functional theory calculations were performed to analyze reaction mechanisms and the obtained results were utilized for further reaction developments. Furthermore, novel sequential synthetic processes were developed by integrating the newly established transition-metal-catalyzed annulations with other reactions, and were applied to the synthesis of derivatives of seco-prezizaane-type sesquiterpeneoid, jiadifenolide, and bioactive heterocyclic compounds, benzosimuline.

Academic Significance and Societal Importance of the Research Achievements

新規遷移金属触媒反応の開発とDFT計算による反応機構解析を組み合わせる研究手法を採用することにより、複雑な多環式化合物や複素環化合物の効率的合成法が確立されたことに加え、魅力的な新規化合物も多数創出された。本研究を通じて、有機合成化学や有機金属化学に関する有用な学術的知見が多数得られ、新たに開発された手法は、天然物合成や生理活性物質合成、材料分野に応用可能な実践的なものであり、新規医薬品や機能材料の開発等に資する社会的意義がある。

Report

(5 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (34 results)

All 2020 2019 2018 2017 2016

All Journal Article (15 results) (of which Peer Reviewed: 15 results,  Open Access: 3 results,  Acknowledgement Compliant: 4 results) Presentation (17 results) (of which Int'l Joint Research: 1 results,  Invited: 2 results) Book (2 results)

  • [Journal Article] Palladium‐Catalyzed [3+2] and [2+2+2] Annulations of 4‐Iodo‐2‐quinolones with Activated Alkynes through Selective C-H Activation2020

    • Author(s)
      Yoshihiko Yamamoto, Jiang Jiyue, Takeshi Yasui
    • Journal Title

      Chemistry A European Journal

      Volume: 26 Issue: 17 Pages: 3749-3757

    • DOI

      10.1002/chem.201904558

    • NAID

      120006848957

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Diastereoselective Methylation at the Congested β-Position of a Butenolide Ring: Studies toward the Synthesis of seco-Prezizaane-Type Sesquiterpenes2019

    • Author(s)
      Tomoyoshi Kawamura, Hirokazu Moriya, Masatoshi Shibuya, Yoshihiko Yamamoto
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 84 Issue: 19 Pages: 12508-12519

    • DOI

      10.1021/acs.joc.9b02017

    • NAID

      120006777553

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Theoretical Study on the Transition-Metal-Catalyzed Cycloadditions of 2H-Azirines with Alkynes: Implication of Carbenoid Intermediates2019

    • Author(s)
      Yoshihiko Yamamoto
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 92 Issue: 3 Pages: 619-628

    • DOI

      10.1246/bcsj.20180344

    • NAID

      130007611377

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of pyrroles via ruthenium-catalyzed nitrogen-transfer [2+2+1] cycloaddition of α,ω-diynes using sulfoximines as nitrene surrogates2018

    • Author(s)
      Kazuma Matsui, Masatoshi Shibuya, Yoshihiko Yamamoto
    • Journal Title

      Communications Chemistry

      Volume: 1 Issue: 1 Pages: 21-21

    • DOI

      10.1038/s42004-018-0022-2

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Theoretical Study of the Copper-Catalyzed Hydroarylation of (Trifluoromethyl)alkyne with Phenylboronic Acid2018

    • Author(s)
      Yoshihiko Yamamoto
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 83 Issue: 20 Pages: 12775-12783

    • DOI

      10.1021/acs.joc.8b02215

    • NAID

      120006554473

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Combined Experimental and Computational Study on Catalytic Cyclocoupling of Epoxides and CO2 Using Porphyrin-Based Cu(II) Metal-Organic Frameworks with 2D Coordination Networks2018

    • Author(s)
      Tsukasa Murayama, Masayuki Asano, Tetsushi Ohmura, Arimitsu Usuki, Takeshi Yasui, Yoshihiko Yamamoto
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 91 Issue: 3 Pages: 383-390

    • DOI

      10.1246/bcsj.20170371

    • NAID

      130006507112

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] The vinylogous Catellani reaction: a combined computational and experimental study2018

    • Author(s)
      Yoshihiko Yamamoto, Jiyue Jiang, Tsukasa Murayama, Masatoshi Shibuya
    • Journal Title

      Chemical Science

      Volume: 9 Issue: 5 Pages: 1191-1199

    • DOI

      10.1039/c7sc04265e

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Recent topics of Cp*RuCl-catalyzed annulation reactions2017

    • Author(s)
      Yoshihiko Yamamoto
    • Journal Title

      Tetrahedron Letters

      Volume: 58 Issue: 40 Pages: 3787-3794

    • DOI

      10.1016/j.tetlet.2017.08.040

    • NAID

      120006375868

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Combined Experimental and Computational Study on Ruthenium(II)-Catalyzed Reactions of Diynes with Aldehydes and N,N-Dimethylformamide2017

    • Author(s)
      Yoshihiko Yamamoto, Yuta Okude, Shota Mori, Masatoshi Shibuya
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 82 Issue: 15 Pages: 7964-7973

    • DOI

      10.1021/acs.joc.7b01229

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Fused Furans and Thiophenes via Ruthenium-Catalyzed Atom-Transfer [2+2+1] Cycloadditions of α,ω-Diynes2017

    • Author(s)
      Yoshihiko Yamamoto
    • Journal Title

      Synlett

      Volume: 28 Issue: 11 Pages: 1250-1257

    • DOI

      10.1055/s-0036-1588767

    • NAID

      120006349127

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Assembly of a Benzo‐Fused Bridged Ketone Scaffold from 1,5,10‐Enediynes through One‐Pot Ruthenium‐Catalyzed Cyclization/Iodine‐Mediated Oxidative Ring Expansion2017

    • Author(s)
      Yoshihiko Yamamoto, Kei‐ichiro Nishimura, Shota Mori, Masatoshi Shibuya
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 56 Issue: 20 Pages: 5494-5497

    • DOI

      10.1002/anie.201700493

    • NAID

      120006331819

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Theoretical Study on Ruthenium-Catalyzed Hydrocarbamoylative Cyclization of 1,6-Diyne with Dimethylformamide2017

    • Author(s)
      Yoshihiko Yamamoto
    • Journal Title

      Organometallics

      Volume: 36 Issue: 6 Pages: 1154-1163

    • DOI

      10.1021/acs.organomet.7b00026

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Ruthenium-Catalyzed Cycloisomerization of 1,6-Diynes with Styryl Terminals Leading to Indenylidene Cycloalkanes2017

    • Author(s)
      Yoshihiko Yamamoto, Kei-ichiro Nishimura, Masatoshi Shibuya
    • Journal Title

      ACS Catalysis

      Volume: 7 Issue: 2 Pages: 1101-1107

    • DOI

      10.1021/acscatal.6b03322

    • NAID

      120006220258

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Ruthenium-catalyzed Hydrocarbamoylative Cyclization of 1,6-Diynes with Formamides2017

    • Author(s)
      Shota Mori, Masatoshi Shibuya, Yoshihiko Yamamoto
    • Journal Title

      Chemistry Letters

      Volume: 46 Issue: 2 Pages: 207-210

    • DOI

      10.1246/cl.160961

    • NAID

      130005317095

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Catalytic [2+2+1] Synthesis of Fused Thiophenes Using Thiocarbonyls as Sulfur Donors Authors2016

    • Author(s)
      Kazuma Matsui, Masatoshi Shibuya, Yoshihiko Yamamoto
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 55 Issue: 49 Pages: 15397-15400

    • DOI

      10.1002/anie.201609545

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] キラルカチオン性ロジウム触媒を用いるエンジインの不斉[2+2+2]付加環化反応の開発2020

    • Author(s)
      安井猛、栗崎晃太郎、山本芳彦
    • Organizer
      日本薬学会第140年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ロジウム触媒を用いるシクロプロパノール含有1,6-ジインの環化異性化反応によるらせん状エキソジエン骨格の合成2020

    • Author(s)
      菊池友宏、安井猛、山本芳彦
    • Organizer
      日本薬学会第140年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ロジウム触媒を用いる炭素-炭素結合活性化に基づくらせん状エキソジエンの合成2019

    • Author(s)
      菊池友宏、安井猛、山本芳彦
    • Organizer
      第65回日本薬学会東海支部大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ロジウム触媒を用いる1,6-ジイン含有シクロプロパノールの環化異性化反応によるらせん状エキソジエン骨格の合成2019

    • Author(s)
      菊池友宏、安井猛、山本芳彦
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ロジウム触媒を用いるエンジインの[2+2+2]環化付加反応による5-6-5三環性ラクトン骨格の不斉合成2019

    • Author(s)
      安井猛、栗崎晃太郎、山本芳彦
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ジアジフェノリドの合成研究:ブテノリドbeta位へのジアステレオ選択的メチル基導入法の開発2019

    • Author(s)
      澁谷正俊、川村智祥、守屋宏一、山本芳彦
    • Organizer
      第45回反応と合成の進歩シンポジウム
    • Related Report
      2019 Annual Research Report
  • [Presentation] DFT計算に導かれたルテニウム触媒反応開発2019

    • Author(s)
      山本芳彦
    • Organizer
      化学反応経路探索のニューフロンティア2019
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] キラルロジウム触媒を用いるエンジインの[2+2+2]環化付加反応による5-6-5三環性ラクトン骨格の不斉合成2019

    • Author(s)
      栗崎晃太朗、安井猛、山本芳彦
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] ロジウム触媒を用いる1,6-ジインの環化異性化反応によるらせん状エキソジエン骨格の合成2019

    • Author(s)
      菊池友宏、安井猛、山本芳彦
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Synthesis of Thiophenes via Ruthenium-Catalyzed [2+2+1] Cyclization of Diynes with Thiocarbonyls2017

    • Author(s)
      Kazuma Matsui, Masatoshi Shibuya, Yoshihiko Yamamoto
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学日吉キャンパス
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] エンジインの[2+2+2]環化付加反応を基軸とする(ー)-jiadifenolideの合成研究2017

    • Author(s)
      川村智祥、澁谷正俊、山本芳彦
    • Organizer
      第35回メディシナルケミストリーシンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] Atom-transfer [2+2+1] Cycloaddition Enabled by Ruthenium Catalysis2017

    • Author(s)
      Yoshihiko Yamamoto
    • Organizer
      International Symposium on Pure & Applied Chemistry (ISPAC)
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] ジアジフェノリドの全合成に向けたモデル研究2017

    • Author(s)
      川村智祥、澁谷正俊、山本芳彦
    • Organizer
      第63回日本薬学会東海支部大会
    • Related Report
      2017 Research-status Report
  • [Presentation] ルテニウム触媒を用いるジインとアルデヒドとの環化付加反応2017

    • Author(s)
      奥出優太、森翔大、澁谷正俊、山本芳彦
    • Organizer
      第63回日本薬学会東海支部大会
    • Related Report
      2017 Research-status Report
  • [Presentation] ルテニウム触媒を用いた1,6-ジインのヒドロカルバモイル化環化反応の開発2016

    • Author(s)
      森翔大、澁谷正俊、山本芳彦
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      早稲田大学
    • Year and Date
      2016-09-14
    • Related Report
      2016 Research-status Report
  • [Presentation] ルテニウム触媒を用いるスチレン末端を有する1,6-ジインの新規環化異性化反応2016

    • Author(s)
      西村佳一郎、澁谷正俊、山本芳彦
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      早稲田大学
    • Year and Date
      2016-09-14
    • Related Report
      2016 Research-status Report
  • [Presentation] ルテニウム触媒を用いるニトロンからシリルジインへの酸素移動型[2 + 2 + 1]環化反応によるシリルフランの合成2016

    • Author(s)
      松井一真,渋谷正俊,山本芳彦
    • Organizer
      日本プロセス化学会2016サマーシンポジウム
    • Place of Presentation
      名古屋
    • Year and Date
      2016-07-28
    • Related Report
      2016 Research-status Report
  • [Book] Spiroketal Phthalane C-Glycosides: Synthesis of Papulacandins and SGLT2 Inhibitors. In Carbohydrate-spiro-heterocycles (Topics in Heterocyclic Chemistry 57)2019

    • Author(s)
      Yoshihiko Yamamoto, Ed, Laszlo Somsak
    • Total Pages
      45
    • Publisher
      Springer Nature
    • ISBN
      9783030319410
    • Related Report
      2019 Annual Research Report
  • [Book] Catalytic Hydroarylation of Carbon-Carbon Multiple Bonds2017

    • Author(s)
      Yoshihiko Yamamoto, Ed, Lutz Ackermann, T. Brent Gunnoe, Laurel Goj Habgood
    • Total Pages
      416
    • Publisher
      Wiley
    • ISBN
      9783527340132
    • Related Report
      2017 Research-status Report

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Published: 2016-07-20   Modified: 2023-03-08  

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