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Development of Highly-Distorted Molecules for Organic Synthetic Chemistry

Research Project

Project/Area Number 19K15586
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionOsaka University

Principal Investigator

Nishii Yuji  大阪大学, 工学研究科, 講師 (70773787)

Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2020: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2019: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Keywordsアライン / ニッケル / ロジウム / 炭素-水素結合活性化 / 複素環化合物 / 環ひずみ / チオフェン / チアゾール / ベンザイン / ニッケル錯体
Outline of Research at the Start

本研究課題は「超環ひずみ分子」の発生手法を確立することで、新たな有機合成手法として応用することを目指す。ここで標的とする分子は、高度にひずんだ三重結合を持つ5員環アラインであり、ベンザインに代表される6員環アラインを活用した化学の発展に対して、手付かずのまま残されてきた未知の分子群といえる。まず、金属錯体化学の視点からアプローチすることにより、様々な5員環アライン分子の存在そのものの証明を試みるともに、その発生手法を最適化することにより、高反応性中間体として、多様な有機合成分野への応用が可能であると期待される。

Outline of Final Research Achievements

Small-membered ring compounds having multiple bonds are valuable reactants for organic synthesis owing to their high ring strain energy. In this study, we investigated the generation method of the five-membered aryne compounds, and attempted to isolate them as metal complexes to determine their structures. In addition, we have developed a new catalytic coupling protocol in which vinylene carbonate was adopted as an oxidizing acetylene surrogate. This reaction system was effective for synthesizing heterocyclic compounds. The reaction mechanism was investigated by computational analysis.

Academic Significance and Societal Importance of the Research Achievements

5員環アライン化合物を金属への配位によって安定化し構造決定することは、長年その存在が議論の対象となっていた高ひずみ分子について新たな知見を与える、学術的に意義深いものといえる。本研究により開発された、炭酸ビニレンをカップリングパートナーとした新たな触媒反応は、従来法で課題となっていた当量酸化剤を必要とせず、合成の難しい無置換の縮環構造を効率的な構築を可能となることは、強力な合成ツールとして広く利用されることが期待される。炭酸のみを副生するという点は、近年課題とされる環境調和性の観点からも優れた技術を開発できたといえる。

Report

(4 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Research-status Report
  • 2019 Research-status Report
  • Research Products

    (26 results)

All 2021 2020 2019 Other

All Journal Article (20 results) (of which Peer Reviewed: 20 results,  Open Access: 3 results) Presentation (5 results) (of which Int'l Joint Research: 1 results,  Invited: 1 results) Remarks (1 results)

  • [Journal Article] Synthesis, Structure, and Chiroptical Properties of Indolo‐ and Pyridopyrrolo‐Carbazole‐Based C2‐Symmetric Azahelicenes2021

    • Author(s)
      T. Taniguchi, U. Nishii, T. Mori, K. Nakayama, M. Miura
    • Journal Title

      Chem. Eur. J.

      Volume: 27 Issue: 26 Pages: 1-7

    • DOI

      10.1002/chem.202100327

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Peri-Selective Direct Acylmethylation and Amidation of Naphthalene Derivatives Using Iridium and Rhodium Catalysts2021

    • Author(s)
      Nishii Yuji、Miura Masahiro、Kona Chandrababu Naidu、Oku Rikuto
    • Journal Title

      Synthesis

      Volume: 53 Issue: 17 Pages: 3126-3136

    • DOI

      10.1055/a-1472-1059

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Electrophilic Substitution of Asymmetrically Distorted Benzenes within Triptycene Derivatives2021

    • Author(s)
      Ueno Keisuke、Nishii Yuji、Miura Masahiro
    • Journal Title

      Organic Letters

      Volume: 23 Issue: 9 Pages: 3552-3556

    • DOI

      10.1021/acs.orglett.1c00970

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rhodium-catalysed direct formylmethylation using vinylene carbonate and sequential dehydrogenative esterification2021

    • Author(s)
      Kato Moena、Ghosh Koushik、Nishii Yuji、Miura Masahiro
    • Journal Title

      Chemical Communications

      Volume: 57 Issue: 67 Pages: 8280-8283

    • DOI

      10.1039/d1cc03362j

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Sulfur-Directed C7-Selective Alkenylation of Indoles under Rhodium Catalysis2021

    • Author(s)
      Kona Chandrababu Naidu、Nishii Yuji、Miura Masahiro
    • Journal Title

      Organic Letters

      Volume: 23 Issue: 16 Pages: 6252-6256

    • DOI

      10.1021/acs.orglett.1c01990

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Benzoisoselenazolones via Rh(III)‐Catalyzed Direct Annulative Selenation by Using Elemental Selenium2021

    • Author(s)
      Xu‐Xu Qing‐Feng、Nishii Yuji、Uetake Yuta、Sakurai Hidehiro、Miura Masahiro
    • Journal Title

      Chemistry - A European Journal

      Volume: 27 Issue: 71 Pages: 17952-17959

    • DOI

      10.1002/chem.202103485

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Optical Properties of Axially Chiral Bibenzo[b]carbazole Derivatives2021

    • Author(s)
      Takishima Ryo、Nishii Yuji、Miura Masahiro
    • Journal Title

      Organic Letters

      Volume: 23 Issue: 4 Pages: 1349-1354

    • DOI

      10.1021/acs.orglett.1c00011

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Metal-Free Direct Trifluoromethylthiolation of Aromatic Compounds Using Triptycenyl Sulfide Catalyst2021

    • Author(s)
      Kurose Ryo、Nishii Yuji、Miura Masahiro
    • Journal Title

      Organic Letters

      Volume: 23 Issue: 6 Pages: 2380-2385

    • DOI

      10.1021/acs.orglett.1c00727

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Oxidative C-H/C-H Annulation of Imidazopyridines and Indazoles through Rhodium-Catalyzed Vinylene Transfer2020

    • Author(s)
      Ghosh Koushik、Nishii Yuji、Miura Masahiro
    • Journal Title

      Organic Letters

      Volume: 22 Issue: 9 Pages: 3547-3550

    • DOI

      10.1021/acs.orglett.0c00975

    • Related Report
      2020 Research-status Report 2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Thioether-Directed C4-Selective C-H Acylmethylation of Indoles Using α-Carbonyl Sulfoxonium Ylides2020

    • Author(s)
      Kona Chandrababu Naidu、Nishii Yuji、Miura Masahiro
    • Journal Title

      Organic Letters

      Volume: 22 Issue: 12 Pages: 4806-4811

    • DOI

      10.1021/acs.orglett.0c01617

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Concise Synthesis of Isocoumarins through Rh-Catalyzed Direct Vinylene Annulation: Scope and Mechanistic Insight2020

    • Author(s)
      Mihara Gen、Ghosh Koushik、Nishii Yuji、Miura Masahiro
    • Journal Title

      Organic Letters

      Volume: 22 Issue: 14 Pages: 5706-5711

    • DOI

      10.1021/acs.orglett.0c02112

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Cp*M-Catalyzed Direct Annulation with Terminal Alkynes and Their Surrogates for the Construction of Multi-Ring Systems2020

    • Author(s)
      Nishii Yuji、Miura Masahiro
    • Journal Title

      ACS Catalysis

      Volume: 10 Issue: 17 Pages: 9747-9757

    • DOI

      10.1021/acscatal.0c02972

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Isothiazoles and Isoselenazoles through Rhodium-Catalyzed Oxidative Annulation with Elemental Sulfur and Selenium2020

    • Author(s)
      Moon Sanghun、Nishii Yuji、Miura Masahiro
    • Journal Title

      Organic Letters

      Volume: 23 Issue: 1 Pages: 49-53

    • DOI

      10.1021/acs.orglett.0c03674

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Benzo[b]thiophenes through Rhodium‐Catalyzed Three‐Component Reaction using Elemental Sulfur2020

    • Author(s)
      Moon Sanghun、Kato Moena、Nishii Yuji、Miura Masahiro
    • Journal Title

      Advanced Synthesis & Catalysis

      Volume: 362 Issue: 8 Pages: 1669-1673

    • DOI

      10.1002/adsc.202000112

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis and circularly polarized luminescence properties of BINOL-derived bisbenzofuro[2,3-b:3’,2’-e]pyridines (BBZFPys)2020

    • Author(s)
      Takishima Ryo、Nishii Yuji、Hinoue Tomoaki、Imai Yoshitane、Miura Masahiro
    • Journal Title

      Beilstein Journal of Organic Chemistry

      Volume: 16 Pages: 325-336

    • DOI

      10.3762/bjoc.16.32

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Copper-Catalyzed Site-Selective Direct Arylation of Triptycene2020

    • Author(s)
      Ueno Keisuke、Nishii Yuji、Miura Masahiro
    • Journal Title

      Chemistry Letters

      Volume: - Issue: 6 Pages: 689-692

    • DOI

      10.1246/cl.200167

    • NAID

      130007852084

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Composite Tetraheteroarylenes and Related Higher Cyclic Oligomers of Heteroarenes Produced by Palladium-Catalyzed Direct Coupling2019

    • Author(s)
      Fukuzumi Keita、Nishii Yuji、Miura Masahiro
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 92 Issue: 12 Pages: 2030-2037

    • DOI

      10.1246/bcsj.20190255

    • NAID

      130007761384

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Rhodium-Catalyzed Annulative Coupling Using Vinylene Carbonate as an Oxidizing Acetylene Surrogate2019

    • Author(s)
      Ghosh Koushik、Nishii Yuji、Miura Masahiro
    • Journal Title

      ACS Catalysis

      Volume: 9 Issue: 12 Pages: 11455-11460

    • DOI

      10.1021/acscatal.9b04254

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Triptycenyl Sulfide: A Practical and Active Catalyst for Electrophilic Aromatic Halogenation Using N-Halosuccinimides2019

    • Author(s)
      Nishii Yuji、Ikeda Mitsuhiro、Hayashi Yoshihiro、Kawauchi Susumu、Miura Masahiro
    • Journal Title

      Journal of the American Chemical Society

      Volume: 142 Issue: 3 Pages: 1621-1629

    • DOI

      10.1021/jacs.9b12672

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Rhodium-Catalyzed Annulative Coupling of Isothiazoles with Alkynes through N-S Bond Cleavage2019

    • Author(s)
      Mihara Gen、Noguchi Teppei、Nishii Yuji、Hayashi Yoshihiro、Kawauchi Susumu、Miura Masahiro
    • Journal Title

      Organic Letters

      Volume: 22 Issue: 2 Pages: 661-665

    • DOI

      10.1021/acs.orglett.9b04437

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] 最高にシンプルな環化カップリング反応の実現を目指して2021

    • Author(s)
      西井祐二
    • Organizer
      第6回有機若手ワークショップ
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] 縮環分子群の迅速構築を志向したビニレントランスファー法の開発2021

    • Author(s)
      西井祐二
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Research-status Report
  • [Presentation] Development of an Efficient Sulfide Catalyst for Aromatic Halogenation2020

    • Author(s)
      Yuji Nishii, Mitsuhiro Ikeda, Yoshihiro Hayashi, Susumu Kawauchi, Masahiro Miura
    • Organizer
      日本化学会 第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] 硫黄配向基を利用したインドールの 位置選択的官能基化手法の開発2019

    • Author(s)
      西井祐二, Chandrababu Naidu Kona, 三浦雅博
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] Iridium-Catalyzed C4- and C7-Selective Direct Alkynylation of Indoles Using Sulfur Directing Groups2019

    • Author(s)
      Yuji Nishii, Chandrababu Naidu Kona, Masahiro Miura
    • Organizer
      20th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Remarks] 反応分子化学領域ホームページ

    • URL

      http://www.chem.eng.osaka-u.ac.jp/~miura-lab/index.html

    • Related Report
      2021 Annual Research Report 2020 Research-status Report

URL: 

Published: 2019-04-18   Modified: 2023-01-30  

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