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Development of One-pot Multifunctionalization of Terminal Alkynes

Research Project

Project/Area Number 16K05694
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Organic chemistry
Research InstitutionKyoto University

Principal Investigator

Miura Tomoya  京都大学, 工学研究科, 准教授 (10378804)

Research Collaborator Funakoshi Yuuta  
Nakamuro Takayuki  
Zhao Qiang  
Miyakawa Sho  
Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2018: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2017: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2016: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywords有機合成化学 / 有機金属化学 / トリアゾール / カルベン錯体 / ロジウム / ニッケル / 不斉合成
Outline of Final Research Achievements

Triazoles are readily prepared by 1,3-dipolar cycloaddition reaction of terminal alkyne and azide. Triazoles have being actively used as a linking site for joining two molecules, especially in the field of biochemistry. On the other hand, few studies tried to use triazoles as a reagent from the viewpoint of organic chemistry. we have discovered that triazoles can be used as a precursor for α-imino carbene species, and reported the cyclization reaction with alkyne in 2009. This report presented the usefulness of triazoles as reagents in the field of organic chemistry and then induced a remarkable number of subsequent studies. Here, we found many of the new reactions developed by using triazoles as a precursor for α-imino carbene species, which can be conducted in one pot from the terminal alkyne as a starting material.

Academic Significance and Societal Importance of the Research Achievements

出発物質として用いる有機化合物が入手容易であることは、有用な反応に不可欠な要件である。しかし有機合成反応の開発研究においては、反応形式の斬新さのみを追求するあまりに、これらの要件が必ずしも満たされないことが多い。本研究では、入手容易な末端アルキンを出発物質として用いて、一つのフラスコに順次あるいは同時に複数の反応基質、反応剤、触媒を作用させ、α-イミノロジウムカルベン種を鍵中間体として利用するワンポット多官能基反応の開発を行った。これらの反応は、一回の後処理と単離精製の操作で目的物を得ることができるため、溶媒、時間、エネルギーなどの大幅な節約につながる環境調和を志向した手法である。

Report

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

    (31 results)

All 2019 2018 2017 2016 Other

All Journal Article (12 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 12 results,  Acknowledgement Compliant: 4 results) Presentation (17 results) (of which Int'l Joint Research: 5 results) Book (1 results) Remarks (1 results)

  • [Journal Article] Photoinduced 1,2-Hydro(cyanomethylation) of Alkenes with a Cyanomethylphosphonium Ylide2019

    • Author(s)
      Miura Tomoya、Murakami Masahiro、Moriyama Daisuke、Funakoshi Yuuta
    • Journal Title

      Synlett

      Volume: 30 Issue: 04 Pages: 511-514

    • DOI

      10.1055/s-0037-1612230

    • NAID

      120006578944

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Elongated Esters from Alkenes2018

    • Author(s)
      Miura Tomoya、Funakoshi Yuuta、Nakahashi Junki、Moriyama Daisuke、Murakami Masahiro
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 57 Issue: 47 Pages: 15455-15459

    • DOI

      10.1002/anie.201809115

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Light/Copper Relay for Aerobic Fragmentation of Lignin Model Compounds2018

    • Author(s)
      Zhou Wang、Nakahashi Junki、Miura Tomoya、Murakami Masahiro
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 7 Issue: 12 Pages: 2431-2434

    • DOI

      10.1002/ajoc.201800520

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Synthesis of γ-Boryl-Substituted Homoallylic Alcohols with anti Stereochemistry Based on a Double-Bond Transposition2018

    • Author(s)
      Miura Tomoya、Nakahashi Junki、Sasatsu Takanori、Murakami Masahiro
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Issue: 4 Pages: 1138-1142

    • DOI

      10.1002/anie.201811205

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Photo-Catalyzed Ortho-Alkylation of Pyridine N-Oxides through Alkene Cleavage2018

    • Author(s)
      Wang Zhou, Tomoya Miura, and Masahiro Murakami
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 57 Issue: 18 Pages: 5139-5142

    • DOI

      10.1002/anie.201801305

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Denitrogenative Annulation of 1H-Tetrazoles with Styrenes Catalyzed by Rhodium2018

    • Author(s)
      Takayuki Nakamuro, Kohei Hagiwara, Tomoya Miura, and Masahiro Murakami
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 57 Issue: 19 Pages: 5497-5500

    • DOI

      10.1002/anie.201801283

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Synthesis of anti-1,2-Oxaborinan-3-enes from Aldehydes and 1,1-Di(boryl)alk-3-enes Using Ruthenium and Chiral Phosphoric Acid Catalysts2017

    • Author(s)
      Tomoya Miura, Junki Nakahashi, Wang Zhou, Yota Shiratori, Scott G. Stewart, and Masahiro Murakami
    • Journal Title

      Journal of the American Chemical Society

      Volume: 139 Issue: 31 Pages: 10903-10908

    • DOI

      10.1021/jacs.7b06408

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Selective Functionalization of Aromatic C(sp2)-H Bonds in the Presence of Benzylic C(sp3)-H Bonds by Electron-Deficient Carbenoid Generated from 4-Acyl-1-sulfonyl-1,2,3-triazoles2017

    • Author(s)
      Tomoya Miura, Qiang Zhao, Masahiro Murakami
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 56 Issue: 52 Pages: 16645-16649

    • DOI

      10.1002/anie.201709384

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Synthesis of 2-Substituted 2-Amino Ketones by Rhodium-Catalyzed Reaction of N-Sulfonyl-1,2,3-triazoles with 2-Alkenols2017

    • Author(s)
      Tomoya Miura, Takamasa Tanaka, Qiang Zhao, Scott G. Stewart, Masahiro Murakami
    • Journal Title

      Helvetica Chimica Acta

      Volume: 100 Issue: 2

    • DOI

      10.1002/hlca.201600320

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Synthesis of Enantiopure C3-Symmetric Triangular Molecules2017

    • Author(s)
      Tomoya Miura, Takayuki Nakamuro, Scott G. Stewart, Yuuya Nagata, and Masahiro Murakami
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 56 Issue: 12 Pages: 3334-3338

    • DOI

      10.1002/anie.201612585

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols Using Palladium and a Chiral Phosphoric Acid2017

    • Author(s)
      Tomoya Miura, Junki Nakahashi, Masahiro Murakami
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 56 Issue: 24 Pages: 6989-6993

    • DOI

      10.1002/anie.201702611

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis of Penta-2,4-dien-1-imines and 1,2-Dihydropyridines by Rhodium-Catalyzed Reaction of N-Sulfonyl-1,2,3-triazoles with 2-(Siloxy)furans2016

    • Author(s)
      Yuuta Funakoshi, Tomoya Miura, Masahiro Murakami
    • Journal Title

      Organic Letters

      Volume: 18 Issue: 24 Pages: 6284-6287

    • DOI

      10.1021/acs.orglett.6b03143

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] 光によるリンイリドからのシアノメチルラジカル種の発生とアルケンへの付加反応2019

    • Author(s)
      ○森山大輔・船越雄太・三浦智也・村上正浩
    • Organizer
      日本化学会第99春季年会(2019)
    • Related Report
      2018 Annual Research Report
  • [Presentation] パラジウムおよびキラルリン酸触媒を用いる1,1-ジ(ボリル)-1-アルケンによるアルデヒドのエナンチオ選択的アリルホウ素化反応2019

    • Author(s)
      ○奥直樹・三浦智也・村上正浩
    • Organizer
      日本化学会第99春季年会(2019)
    • Related Report
      2018 Annual Research Report
  • [Presentation] Synthesis of γ-Boryl-Substituted anti-Homoallylic Alcohols from Terminal Alkynes, Aldehydes, and Diborons2018

    • Author(s)
      〇Junki Nakahashi, Takanori Sasatsu, Tomoya Miura, Masahiro Murakami
    • Organizer
      JGP Chem & ChemEn International Workshop: Sustainability-Oriented Organic Synthesis
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 可視光レドックス触媒を用いたリンイリドからの(アルコキシカルボニル)メチルラジカルの生成とアルケンへの付加反応の開発2018

    • Author(s)
      〇三浦智也・船越雄太・中橋惇貴・森山大輔・村上正浩
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] NH-テトラゾールとスチレンによる3,5-ジアリール-2-ピラゾリンの不斉合成2018

    • Author(s)
      ○中室貴幸・萩原康平・三浦智也・村上正
    • Organizer
      日本化学会第98春季年会(2018)
    • Related Report
      2017 Research-status Report
  • [Presentation] Rhodium-Catalyzed Intramolecular C-H Functionalization of Acceptor/acceptor Carbenoids Generated from 4-Acyl-1-sulfonyl-1,2,3-triazoles2018

    • Author(s)
      ○ZHAO, Qiang; MIURA, Tomoya; MURAKAMI Masahiro
    • Organizer
      日本化学会第98春季年会(2018)
    • Related Report
      2017 Research-status Report
  • [Presentation] ルテニウムおよびキラルリン酸触媒を用いた1,1-ジボリルアルカ-3-エンとアルデヒドによるanti-1,2-オキサボリナン-3-エンのエナンチオ選択的合成2018

    • Author(s)
      ○中橋惇貴・白鳥陽太・三浦智也・村上正浩
    • Organizer
      日本化学会第98春季年会(2018)
    • Related Report
      2017 Research-status Report
  • [Presentation] 1,1-ジボリル-アルカ-3-エンからニッケル触媒を用いた二重結合の移動による(Z)-アリルホウ酸エステルの生成とそのアリル化反応2018

    • Author(s)
      ○白鳥陽太・中橋惇貴・三浦智也・村上正浩
    • Organizer
      日本化学会第98春季年会(2018)
    • Related Report
      2017 Research-status Report
  • [Presentation] Ortho-Alkylation of Pyridine N-Oxide by Photo-Catalyzed Alkene Cleavage2018

    • Author(s)
      ○ZHOU, Wang; MIURA, Tomoya; MURAKAMI, Masahiro
    • Organizer
      日本化学会第98春季年会(2018)
    • Related Report
      2017 Research-status Report
  • [Presentation] Rhodium-Catalyzed Functionalization of Aromatic C-H Bonds with 4-Acyl-1-mesyl-1,2,3-triazoles2017

    • Author(s)
      ○Qiang Zhao, Tomoya Miura, Masahiro Murakami
    • Organizer
      Nordic / Kyoto OMCOS2017
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Rhodium-Catalyzed Functionalization of Aromatic C-H Bonds with 4-Acyl-1-mesyl1,2,3-triazoles2017

    • Author(s)
      ○Qiang Zhao, Tomoya Miura, Masahiro Murakami
    • Organizer
      the 19th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 19 )
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols by Relay Work of Palladium and Chiral Phosphoric Acid upon 1,1-Di(boryl)alk-3-enes and Aldehydes2017

    • Author(s)
      ○Junki Nakahashi, Tomoya Miura, Masahiro Murakami
    • Organizer
      the 19th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 19 )
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] 1,1-ジボリルアルカ-3-エンから二重結合の移動によるアリルホウ酸エステルの生成とその反応2017

    • Author(s)
      ○中橋惇貴、三浦智也、村上正浩
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] ロジウム触媒を用いるビニルアリール基置換トリアゾールの不斉環化オリゴマー化反応2017

    • Author(s)
      ○中室貴幸、石原優実、長田裕也、三浦智也、村上正浩
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] トリアゾールをカルベン前駆体として利用した触媒反応2017

    • Author(s)
      ○三浦智也・船越雄太・中室貴幸・宮川 翔・藤本佳寿・村上正浩
    • Organizer
      第7回 複素環化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] In Situ Generation of Allylboron Reagents from 1,1-Di(boryl)alk-3-enes and Their Reactions with Aldehydes2017

    • Author(s)
      Tomoya Miura
    • Organizer
      The 12th International Conference on Cutting-Edge Organic Chemistry in Asia(ICCEOCA-12)
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] 脂肪族末端アルケンのロジウム触媒脱水素ホウ素化反応2016

    • Author(s)
      三浦智也
    • 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
  • [Book] Rhodium Catalysis in Organic Synthesis: Methods and Reactions2019

    • Author(s)
      T. Miura and M. Murakami
    • Total Pages
      688
    • Publisher
      Wiley-VCH
    • ISBN
      9783527343645
    • Related Report
      2018 Annual Research Report
  • [Remarks] 京都大学村上研究室ホームページ

    • URL

      http://www.sbchem.kyoto-u.ac.jp/murakami-lab/publications/publ_miura.html

    • Related Report
      2018 Annual Research Report 2017 Research-status Report

URL: 

Published: 2016-04-21   Modified: 2020-03-30  

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