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Selective Recognition of Aromatic or Aliphatic Compounds; Utilization of Weak Ineraction on Multi and Suitable Positons

Research Project

Project/Area Number 18K19079
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 33:Organic chemistry and related fields
Research InstitutionOsaka University

Principal Investigator

Yasuda Makoto  大阪大学, 工学研究科, 教授 (40273601)

Project Period (FY) 2018-06-29 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000)
Fiscal Year 2019: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
Fiscal Year 2018: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Keywords選択性 / 芳香族 / 相互作用 / ルイス酸 / 配位子
Outline of Final Research Achievements

Selective recognition between aromatic and aliphatic compounds has never been realized under catalytic conditions. In this research project, the ligand based on tris(phenoxy) framework acted as an effective structure for boron complexes in the reaction of the selective reaction of aromatic/aliphatic compounds. The substituents at the ortho-position of phenoxy group contributed to the selectivity and many types of the substituents were investigated. A large number of the relationship between the substituents and selectivity were obtained and important information of the ligand design was confirmed. Machine learning was applied to the ligand design based on the data of the relationship. It proposed the suitable structure for high selectivity and the new complex was experimentally synthesized. It gave the highest selectivity, and under low temperature the exclusive formation from aromatic compounds was attained.

Academic Significance and Societal Importance of the Research Achievements

有機合成において、複数の原料混合物から選択的にひとつの原料を反応せること、すなわち化学選択的反応は究極の課題である。これまで、大きく特徴の異なる化合物間での選択的反応は達成されてきたが、有機化合物の代表である芳香族化合物と脂肪族化合物を見分ける反応は前例がなかった。本研究ではこのテーマに取り組み、世界で初めて芳香族と脂肪族の混合系から、極めて高い選択性で芳香族化合物を認識する触媒反応を達成した。このことは、従来高いコストのかかっていた化合物分離や、多段階の変換反応を全く必要とせず、今回開発した化合物を触媒として少量添加するだけで達成することができ、学術的にも工業的にも画期的な成果である。

Report

(4 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • 2018 Research-status Report
  • Research Products

    (22 results)

All 2020 2019 2018

All Journal Article (15 results) (of which Peer Reviewed: 15 results,  Open Access: 2 results) Presentation (7 results) (of which Int'l Joint Research: 5 results,  Invited: 7 results)

  • [Journal Article] Characterization of Highly Coordinated Allylgermanes: Pivotal Players for Enhanced Nucleophilicity and Stereoselectivity2020

    • Author(s)
      Minami Yohei、Nishida Kento、Konishi Akihito、Yasuda Makoto
    • Journal Title

      Chemistry - An Asian Journal

      Volume: - Issue: 12 Pages: 1852-1857

    • DOI

      10.1002/asia.202000392

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] anti-Carbometalation of Alkynyl Sulfides Using Indium Tribromide and Ketene Silyl Acetals2020

    • Author(s)
      Kang Kyoungmin、Sakamoto Kosuke、Nishimoto Yoshihiro、Yasuda Makoto
    • Journal Title

      Chemistry Letters

      Volume: 49 Issue: 10 Pages: 1136-1139

    • DOI

      10.1246/cl.200400

    • NAID

      130007923175

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] InBr3‐Catalyzed Coupling Reaction between Electron‐Deficient Alkenyl Ethers with Silyl Enolates for Stereoselective Synthesis of 1,5‐Dioxo‐alk‐2‐enes2020

    • Author(s)
      Nakao Shuichi、Saikai Miki、Nishimoto Yoshihiro、Yasuda Makoto
    • Journal Title

      European Journal of Organic Chemistry

      Volume: 2021 Issue: 1 Pages: 77-81

    • DOI

      10.1002/ejoc.202001342

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] (o‐Phenylenediamino)borylstannanes: Efficient Reagents for Borylation of Various Alkyl Radical Precursors2020

    • Author(s)
      Suzuki Kensuke、Nishimoto Yoshihiro、Yasuda Makoto
    • Journal Title

      Chemistry-A European Journal

      Volume: 27 Issue: 12 Pages: 3968-3973

    • DOI

      10.1002/chem.202004692

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Cycloisomerization of Conjugated Bisbutatrienes into Pentalene Skeletons: Synthesis and Properties of Bisbutatrienes with an Acenaphthene Backbone2020

    • Author(s)
      Konishi Akihito、Satake Shoya、Yasuda Makoto
    • Journal Title

      Chemistry Letters

      Volume: 49 Issue: 5 Pages: 589-592

    • DOI

      10.1246/cl.200121

    • NAID

      130007840177

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Carbometalation and Heterometalation of Carbon‐Carbon Multiple‐Bonds Using Group‐13 Heavy Metals: Carbogallation, Carboindation, Heterogallation, and Heteroindation2020

    • Author(s)
      Nishimoto Yoshihiro、Yasuda Makoto
    • Journal Title

      Chemistry An Asian Journal

      Volume: 15 Issue: 6 Pages: 636-650

    • DOI

      10.1002/asia.201901730

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis of (Z)‐β‐(Carbonylamino)alkenylindium through Regioselective anti‐Carboindation of Ynamides and Its Transformation to Multisubstituted Enamides2020

    • Author(s)
      Kang Kyoungmin、Sakamoto Kosuke、Nishimoto Yoshihiro、Yasuda Makoto
    • Journal Title

      Chemistry A European Journal

      Volume: 26 Issue: 22 Pages: 4930-4934

    • DOI

      10.1002/chem.201905175

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of α-Alkenyl α,β-Unsaturated Ketones via Dehydrogermylation of Oxagermacycles with Regeneration of the Germanium(II) Species2019

    • Author(s)
      Minami Yohei、Konishi Akihito、Yasuda Makoto
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 24 Pages: 9818-9823

    • DOI

      10.1021/acs.orglett.9b03454

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Cage-Shaped Aluminum Aryloxides: Efficient Lewis Acid Catalyst for Stereoselective Glycosylation Driven by Flexible Shift of Four- to Five-Coordination2019

    • Author(s)
      Tanaka Daiki、Kadonaga Yuichiro、Manabe Yoshiyuki、Fukase Koichi、Sasaya Shota、Maruyama Hikaru、Nishimura Sota、Yanagihara Mayu、Konishi Akihito、Yasuda Makoto
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Issue: 44 Pages: 17466-17471

    • DOI

      10.1021/jacs.9b08875

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Regioselective Synthesis of 5-Metalated 2-Pyrones by Intramolecular Oxymetalation of Carbonyl-ene-yne Compounds Using Indium Trihalide2019

    • Author(s)
      Yata Tetsuji、Kita Yuji、Nishimoto Yoshihiro、Yasuda Makoto
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 84 Issue: 21 Pages: 14330-14341

    • DOI

      10.1021/acs.joc.9b02186

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Regio- and Stereoselective Carboindation of Internal Alkynyl Ethers with Organosilicon or -stannane Nucleophiles2019

    • Author(s)
      Kang Kyoungmin、Nishimoto Yoshihiro、Yasuda Makoto
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 84 Issue: 21 Pages: 13345-13363

    • DOI

      10.1021/acs.joc.9b01505

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Geometrically Selective Synthesis of (E)-Enamides via Radical Allylation of Alkyl Halides with α-Aminoallylic Stannanes2019

    • Author(s)
      Suzuki Kensuke、Nishimoto Yoshihiro、Yasuda Makoto
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 17 Pages: 6589-6592

    • DOI

      10.1021/acs.orglett.9b01744

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Characterization of Pheox- and Phebox-Aluminum Complexes: Application as Tunable Lewis Acid Catalysts in Organic Reactions2019

    • Author(s)
      Nishimoto Yoshihiro、Nakao Shuichi、Machinaka Shota、Hidaka Fumiko、Yasuda Makoto
    • Journal Title

      Chemistry A European Journal

      Volume: 25 Issue: 46 Pages: 10792-10796

    • DOI

      10.1002/chem.201901791

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Open-Shell and Antiaromatic Character Induced by the Highly Symmetric Geometry of the Planar Heptalene Structure: Synthesis and Characterization of a Nonalternant Isomer of Bisanthene2019

    • Author(s)
      Konishi Akihito、Horii Koki、Shiomi Daisuke、Sato Kazunobu、Takui Takeji、Yasuda Makoto
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Issue: 26 Pages: 10165-10170

    • DOI

      10.1021/jacs.9b04080

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Enhancement of Antiaromatic Character via Additional Benzoannulation into Dibenzo[a,f]pentalene: Syntheses and Properties of Benzo[a]naphtho[2,1-f]pentalene and Dinaphtho[2,1-a,f]pentalene2019

    • Author(s)
      Akihito Konishi, Yui Okada, Ryohei Kishi, Masayoshi Nakano, Makoto Yasuda
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 141 Issue: 1 Pages: 560-571

    • DOI

      10.1021/jacs.8b11530

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Presentation] 有機典型金属反応剤の構造と選択性2020

    • Author(s)
      安田 誠
    • Organizer
      日本化学会近畿支部北陸地区講演会と研究発表会
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] Cage-shaped Aluminum Aryloxides as a Lewis Acid Catalyst2019

    • Author(s)
      Makoto Yasuda
    • Organizer
      The 1st Symposium for the Distinguished Lectureship Awards on The International Cutting-Edge Organic Chemistry in Asia
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Germyl EnolatesCharacterizations, Structures and Reactivity of Stereoselective Aldol Reactions2019

    • Author(s)
      Makoto Yasuda
    • Organizer
      International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (ICCOC-GTL-16)
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Cage-Shaped Aluminum Lewis Acid Catalyst for Selective Reactions2019

    • Author(s)
      Makoto Yasuda
    • Organizer
      The 18th Asian Chemical Congress and the 20th General AssembIy of the Federation of Asian Chemical Socieities (ACC 2019)- Joint FACS/IUPAC ChemRAWN Symposium on Green Catalysis
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Regio- and Stereoselective Synthesis of Functionalized Organic Compounds via Main Group Organometallic Compounds2018

    • Author(s)
      Makoto Yasuda
    • Organizer
      The University of Hong Kong -Osaka University, 2nd Joint Symposium on Materials Research - Diverse Aspects of Future Chemistry -
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 典型金属の性状制御2018

    • Author(s)
      安田 誠
    • Organizer
      第5回 新学術領域研究「反応集積化が導く中分子戦略:高次生物機能分子の創製」若手シンポジウム
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] Lewis Acidity of Borates Controlled by Their Cage-Structure2018

    • Author(s)
      Makoto Yasuda
    • Organizer
      Strasbourg University -Osaka University, Joint Symposium on “Diverse Facets of Chemistry II”
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research / Invited

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Published: 2018-07-25   Modified: 2022-01-27  

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