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Photo-induced site-selective deoxigenation and functionalization of sugars

Research Project

Project/Area Number 19K15562
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionKyoto University

Principal Investigator

Masuda Yusuke  京都大学, 工学研究科, 特定助教 (20822307)

Project Period (FY) 2019-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2020: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2019: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywords糖 / 水 / 光 / イリジウム / 光酸化還元触媒 / 光反応 / 無保護 / 脱酸素化 / 位置選択的官能基化 / ケトン
Outline of Research at the Start

本研究では、光とケトン触媒を用いた糖の2位選択的脱ヒドロキシル化および官能基化反応の開発を行う。すなわち、グルコースに対して水中で光励起されたケトンを作用させることで、水素引き抜きとラジカルの転位を経て、2―デオキシグルコノラクトンへと変換する。また、生成するラジカル中間体を他の反応剤で補足することにより、糖の2位選択的官能基化を行う。これによって、従来は保護・脱保護を含む多段階の合成を必要としていた糖の2位における置換反応を、極めて簡便に行うことができる。

Outline of Final Research Achievements

Sugars play an essential role in biological functions, and it is highly desired to develop the methods for efficiently transforming these natural compounds in synthetic organic chemistry. In this study, we developed the direct conversion of unprotected sugars by photo-irradiation in water: Unprotected aldoses such as glucose and ribose were directly transformed to 2-deoxysugars under photo-irradiation by using water-soluble ketone as a catalyst. Furthermore, a water-soluble iridium photocatalyst found to be more efficient for photo-isomerization of sugars, and a wide range of sugars could be converted to the corresponding 2-deoxysugars under mild reaction conditions. Deoxysugars are an important class of natural compounds found in DNA and erythromycin, and they can be directly synthesized from readily available unprotected sugars by the present method.

Academic Significance and Societal Importance of the Research Achievements

本研究は、水中での光反応が糖類の変換に効果的であることを示した点で学術的意義が大きい。従来の有機溶媒中での反応では、糖類を適切に修飾することでその溶解性や反応性を制御していた。しかし、修飾過程における行程数や廃棄物の増加が問題であった。一方本研究では光を用いることで、有機溶媒の使用と反応前修飾の二つの問題を解決し、高効率かつ高付加価値な糖類変換反応を達成した。本手法は既存の糖類の合成を効率化するだけでなく、新規糖類縁体の合成に役立つことから、医薬や材料など幅広い分野への波及効果が期待できる。

Report

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

    (15 results)

All 2021 2020 2019

All Journal Article (10 results) (of which Peer Reviewed: 10 results,  Open Access: 1 results) Presentation (5 results)

  • [Journal Article] Photo‐Induced Dihydroxylation of Alkenes with Diacetyl, Oxygen, and Water2021

    • Author(s)
      Masuda Yusuke、Ikeshita Daichi、Murakami Masahiro
    • Journal Title

      Helvetica Chimica Acta

      Volume: 104 Issue: 3

    • DOI

      10.1002/hlca.202000228

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Dehydrative/Decarboxylative Coupling of Carboxylic Acids with Allylic Alcohols2021

    • Author(s)
      Masuda Yusuke、Ito Misato、Murakami Masahiro
    • Journal Title

      Chemistry Letters

      Volume: - Issue: 5 Pages: 1030-1033

    • DOI

      10.1246/cl.210036

    • NAID

      130008040448

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Dehydrative Allylation of α C(sp3)-H Bonds of Alkylamines with Allylic Alcohols2020

    • Author(s)
      Masuda Yusuke、Ito Misato、Murakami Masahiro
    • Journal Title

      Organic Letters

      Volume: 22 Issue: 11 Pages: 4467-4470

    • DOI

      10.1021/acs.orglett.0c01464

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Degradation of Unprotected Aldohexonic Acids to Aldopentoses Promoted by Light and Oxygen2020

    • Author(s)
      Masuda Yusuke、Ito Misato、Murakami Masahiro
    • Journal Title

      Chemistry Letters

      Volume: 49 Issue: 11 Pages: 1309-1311

    • DOI

      10.1246/cl.200517

    • NAID

      130007936950

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Photoinduced Dearomatizing Three‐Component Coupling of Arylphosphines, Alkenes, and Water2020

    • Author(s)
      Masuda Yusuke、Tsuda Hiromu、Murakami Masahiro
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Issue: 7 Pages: 3551-3555

    • DOI

      10.1002/anie.202013215

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] C1 Oxidation/C2 Reduction Isomerization of Unprotected Aldoses Induced by Light/Ketone2020

    • Author(s)
      Masuda Yusuke、Tsuda Hiromu、Murakami Masahiro
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 59 Issue: 7 Pages: 2755-2759

    • DOI

      10.1002/anie.201914242

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] A Strained Vicinal Diol as a Reductant for Coupling of Organyl Halides2019

    • Author(s)
      Ishida Naoki、Masuda Yusuke、Sun Fangzhu、Kamae Yoshiki、Murakami Masahiro
    • Journal Title

      Chemistry Letters

      Volume: 48 Issue: 9 Pages: 1042-1045

    • DOI

      10.1246/cl.190403

    • NAID

      130007703046

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Photo-assisted Fixation of CO2 onto Aryl Bromides Producing Aromatic Esters2019

    • Author(s)
      Ishida Naoki、Masuda Yusuke、Liao Wenqing、Murakami Masahiro
    • Journal Title

      Chemistry Letters

      Volume: 48 Issue: 11 Pages: 1316-1318

    • DOI

      10.1246/cl.190563

    • NAID

      130007741801

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Tofisopam by Way of Photoinduced CO2 Fixation2019

    • Author(s)
      Masuda Yusuke、Makita Katsuhiko、Ishida Naoki、Murakami Masahiro
    • Journal Title

      Chemistry ? An Asian Journal

      Volume: 14 Issue: 23 Pages: 4189-4192

    • DOI

      10.1002/asia.201901431

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Carboxylation of Benzylic and Aliphatic C?H Bonds with CO2 Induced by Light/Ketone/Nickel2019

    • Author(s)
      Ishida Naoki、Masuda Yusuke、Imamura Yuuya、Yamazaki Katsushi、Murakami Masahiro
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Issue: 50 Pages: 19611-19615

    • DOI

      10.1021/jacs.9b12529

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] 水溶性イリジウム光酸化還元触媒を用いたD-グルコースの2-デオキシ-D-グルコン酸への光異性化反応2021

    • Author(s)
      津田裕睦、増田侑亮、村上正浩
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] アリールホスフィン、アルケン、および水の脱芳香族三成分カップリング反応2021

    • Author(s)
      増田侑亮、津田裕睦、村上正浩
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] カルボン酸とアリルアルコールの脱水/脱炭酸型カップリング反応2021

    • Author(s)
      伊藤京、増田侑亮、村上正浩
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] ジアセチル・酸素・水によるアルケンの光ジヒドロキシル化反応2021

    • Author(s)
      池下大智、増田侑亮、村上正浩
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Light/Palladium Promoted Benzylic Acylation and Allylation of 2-Alkylbenzophenones2020

    • Author(s)
      増田侑亮、蒔田克彦、石田直樹、村上正浩
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report

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Published: 2019-04-18   Modified: 2022-01-27  

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