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Creation of Artificial Biocatalysts with NHC and Application to Organic Synthesis

Research Project

Project/Area Number 25288078
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypePartial Multi-year Fund
Section一般
Research Field Bio-related chemistry
Research InstitutionOkayama University

Principal Investigator

Ema Tadashi  岡山大学, 自然科学研究科, 教授 (20263626)

Project Period (FY) 2013-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥17,940,000 (Direct Cost: ¥13,800,000、Indirect Cost: ¥4,140,000)
Fiscal Year 2017: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Fiscal Year 2016: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Fiscal Year 2015: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Fiscal Year 2014: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Fiscal Year 2013: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Keywords生体触媒 / 有機触媒 / 含窒素複素環式カルベン / 無溶媒 / 酵素 / 酵素反応 / 人工酵素 / 触媒・化学プロセス / 生体機能利用 / 化学修飾 / 人工生体触媒
Outline of Final Research Achievements

We created an artificial biocatalyst capable of catalyzing the C-C bond formation. To enable the binding to the catalytic serine residue of the active site of a lipase, NHC precursor 1 bearing a phosphate group (transition-state analog) was synthesized in 13 steps. Artificial biocatalyst CALB-1 was obtained by mixing 1 with a lipase, and it catalyzed the asymmetric benzoin reaction. We also demonstrated that enzymatic properties such as enantioselectivity could be controlled by the chemical modification of the I287C variant of a lipase. We also found that the catalyst loading of NHC can be reduced under solvent-free conditions. Even solid-to-solid or solid-to-liquid conversions took place with low catalyst loading (0.2 mol%), and even semi-solid state organocatalysis took place.

Academic Significance and Societal Importance of the Research Achievements

C-C結合形成反応を触媒できる汎用酵素は極めて希である。生体触媒は、環境に優しく持続的発展を可能にする技術の1つであるが、C-C結合形成反応を触媒できるものが少ないため、これを打破する革新的手法が待ち望まれていた。本研究では、C-C結合形成反応を触媒できる活性種として含窒素複素環式カルベン(NHC)を選択し、NHC前駆体をタンパク質反応場であるリパーゼに導入することにより、人工生体触媒を創成し、実際にC-C結合形成反応を触媒することを確認した。C-C結合形成反応を触媒する人工生体触媒を創成できることを実証した本研究の意義は極めて大きい。

Report

(7 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • 2015 Annual Research Report
  • 2014 Annual Research Report
  • 2013 Annual Research Report
  • Research Products

    (11 results)

All 2018 2017 2016 2015 2014

All Journal Article (2 results) (of which Peer Reviewed: 2 results,  Acknowledgement Compliant: 2 results,  Open Access: 1 results) Presentation (9 results)

  • [Journal Article] Solvent-Free Benzoin and Stetter Reactions with a Small Amount of NHC Catalyst in the Liquid or Semisolid State2016

    • Author(s)
      Tadashi Ema, Yoshiko Nanjo, Sho Shiratori, Yuta Terao, Ryo Kimura
    • Journal Title

      Organic Letters

      Volume: 18 Issue: 21 Pages: 5764-5767

    • DOI

      10.1021/acs.orglett.6b03115

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Chemical Modification of Lipase for Rational Enhancement of Enantioselectivity2015

    • Author(s)
      Tadashi Ema, Hiroki Inoue
    • Journal Title

      Chemistry Letters

      Volume: 44 Issue: 10 Pages: 1374-1376

    • DOI

      10.1246/cl.150667

    • NAID

      130005101495

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Presentation] 効率的利用を目指したNHC触媒反応の条件検討2018

    • Author(s)
      岩井健太,小野真一,南條喜子,前田千尋,高石和人,依馬 正
    • Organizer
      2018年日本化学会中国四国支部大会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 微量のNHC触媒を用いる無溶媒benzoin反応とStetter反応2017

    • Author(s)
      小野真一,南條喜子,前田千尋,高石和人,依馬 正
    • Organizer
      第28回基礎有機化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] ペンタフルオロフェニル基を有するNHC有機触媒を用いた無溶媒benzoin反応とStetter反応2017

    • Author(s)
      小野真一,南條喜子,前田千尋,高石和人,依馬 正
    • Organizer
      第44回有機典型元素化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 無溶媒で液体または固体の基質を用いるNHC有機触媒反応2017

    • Author(s)
      小野真一,南條喜子,前田千尋,高石和人,依馬 正
    • Organizer
      日本化学会中国四国支部大会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 微量のNHC有機触媒を用いる無溶媒ベンゾイン反応とStetter反応2017

    • Author(s)
      白鳥 翔,南條喜子,前田千尋,高石和人,依馬 正
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      横浜
    • Related Report
      2016 Annual Research Report
  • [Presentation] NHC有機触媒を用いた無溶媒ベンゾイン反応2016

    • Author(s)
      南條喜子,寺尾雄太,木村 涼,前田千尋,高石和人,依馬 正
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学
    • Year and Date
      2016-03-25
    • Related Report
      2015 Annual Research Report
  • [Presentation] Creation of Chemically Modified Lipases and Application to Organic Synthesis2014

    • Author(s)
      Hiroki Inoue, Chihiro Maeda, Tadashi Ema
    • Organizer
      Active Enzyme Molecule 2014
    • Place of Presentation
      富山
    • Year and Date
      2014-12-18
    • Related Report
      2014 Annual Research Report
  • [Presentation] 有機合成への応用を目的とした化学修飾リパーゼの創成2014

    • Author(s)
      井上浩希,前田千尋,依馬 正
    • Organizer
      第8回バイオ関連化学シンポジウム
    • Place of Presentation
      岡山
    • Year and Date
      2014-09-11
    • Related Report
      2014 Annual Research Report
  • [Presentation] 化学修飾リパーゼの創成と有機合成への応用2014

    • Author(s)
      井上浩希,前田千尋,依馬 正
    • Organizer
      モレキュラー・キラリティー2014
    • Place of Presentation
      仙台
    • Year and Date
      2014-06-07
    • Related Report
      2014 Annual Research Report

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Published: 2013-05-21   Modified: 2020-03-30  

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