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marine natural products synthesis based on the hypothesis of biosynhtesis

Research Project

Project/Area Number 16K01916
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Biomolecular chemistry
Research InstitutionKochi University

Principal Investigator

Ichikawa Yoshiyasu  高知大学, 教育研究部自然科学系理工学部門, 教授 (60193439)

Co-Investigator(Kenkyū-buntansha) 細川 誠二郎  早稲田大学, 理工学術院, 准教授 (10307712)
Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2018: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2017: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2016: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywords海洋天然物 / 全合成 / 生合成 / イソシアニド / Ugi 反応 / テルペン / Passerini 反応 / 天然物合成 / Ugi反応 / Passerini反応 / イソニトリルテルペン / 天然物 / 生合成仮説 / 天然物化学 / 有機合成 / Ugi反応 / アミノ酸 / 生物活性分子 / 有機合成化学
Outline of Final Research Achievements

One-pot biomimetic synthesis of halichonadin Q and M, using the Ugi reaction (U-5C-4CR), were executed. A unique pathway for the biosynthesis of the marine sponge terpenes, exigurin and boneratamides A-C, is proposed. Based on these proposals, a biomimetic strategy using key Ugi coupling reactions bewteen terpene isocyanides and amino acids was developed for construction of the core structures of exigurin, boneratamides A,halichonadin Q and M. A pathway is proposed for the biosynthesis of the unique homo-dimeric terpene, halichonadin H. The proposed biosynthesis pathway involves the two key Passerini reactions of eudesamane-type terpene isocyanides. Passerini reaction of model terpene isocyanide and formaldehyde afforded α-hydroxy acetamide, which was further subjected to oxidation and second Passerini reaction. This reaction sequence furnished α-hydroxy-malonamide that have an identical structural motif in halichonadin H.

Academic Significance and Societal Importance of the Research Achievements

低分子誘導体のライブラリーを構築する手法としてUgi反応は注目を集め,製薬やマテリアル科学の研究分野で活発に汎用されている。これに対して,「自然界が代謝産物の多様性を獲得するためにUgi反応を用いている」という仮説は,広く認知されていない。生体内のUgi反応をテーマとした研究は,これから大きく発展することが期待できる。例えば,生体内でUgi反応を司ると考えられる未知の酵素 ‘ウギアーゼ’の探索は,未開拓の研究テーマである。さらに,「生合成に学んだ低分子誘導体のライブラリー構築」は,多成分連結反応の新展開として期待できる。

Report

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

    (13 results)

All 2019 2018 2017 2016

All Journal Article (6 results) (of which Peer Reviewed: 6 results,  Acknowledgement Compliant: 4 results) Presentation (7 results)

  • [Journal Article] 17.THE DAWN, EVOLUTION AND PERSONAL REMINISCENCES IN STUDIES OF GLYCOSYL ISOCYANATES AND ISOCYANIDES2018

    • Author(s)
      Ichikawa, Y.
    • Journal Title

      Heterocycles

      Volume: 96 Issue: 10 Pages: 1691-1728

    • DOI

      10.3987/rev-18-892

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Bioinspired Synthesis of the Central Core of Halichonadin H: The Passerini Reaction in a Hypothetical Biosynthesis of Marine Natural Products2018

    • Author(s)
      Yoshiyasu Ichikawa,Toshiba Yamasaki, Keisuke Nakanishi, Yutaro Utagawa, Seijiro Hosokawa,Toshiya Masuda
    • Journal Title

      Synthesis

      Volume: 5 Issue: 11 Pages: 2305-2310

    • DOI

      10.1055/s-0037-1610867

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Trityl cation catalyzed intramolecular carbonyl-ene cyclization and [2+2] cycloaddition2017

    • Author(s)
      Nomoto, Y.; Horinouchi, R.; Nishiyama, N.; Nakano, K.; Ichikawa, Y.; KOTSUKI, H.
    • Journal Title

      Synlett

      Volume: 28 Issue: 02 Pages: 265-269

    • DOI

      10.1055/s-0036-1588618

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis of trans-2,6-piperidinedicarboxamide using the Ugi reaction. A plausible model for the biosynthesis of halichonadin P2016

    • Author(s)
      Mimura, R.; Kitamori, A.; Nakano, K.; KOTSUKI, H.; Matsumoto, K.; Kaneno, D.; Masuda, T.; Ichikawa, Y.
    • Journal Title

      Heterocycles

      Volume: 92 Issue: 5 Pages: 857-865

    • DOI

      10.3987/com-16-13422

    • NAID

      40020825865

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] A biomimetic approach to the synthesis of terpene-amino acid conjugates. The Ugi reaction in the hypothetical biosynthesis of marine natural products2016

    • Author(s)
      Ichikawa, Y.; Saito, K.; Mimura, R.; Kitamori, A.; Matsukawa, A.; Ikeda, A.; Masuda, T.; KOTSUKI, H.; Nakano, K.
    • Journal Title

      Heterocycles

      Volume: 92 Issue: 6 Pages: 1040-1053

    • DOI

      10.3987/com-16-13442

    • NAID

      40020862298

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis of beta-glycosyl formamides through N-glycosylation of unprotected carbohydrates2016

    • Author(s)
      Ichikawa, Y.; Matsukawa, A.; Maeda, M.; Tomita,Y.; Mimura, R.; Kitamori, A.; KOTSUKI, H.; Nakano, K.; Masuda, T.
    • Journal Title

      Heterocycles

      Volume: 92 Issue: 12 Pages: 2201-2212

    • DOI

      10.3987/com-16-13584

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] 転位反応を活用した天然物の合成2019

    • Author(s)
      市川 善康、森本 裕詞、山﨑 季樹
    • Organizer
      日本農芸化学会2019年度大会
    • Related Report
      2018 Annual Research Report
  • [Presentation] イグジグリンの合成研究2019

    • Author(s)
      中西啓介,前田充俊,佐藤誠也,宇田川裕多郎,細川誠二郎,市川 善康
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] テルペンの合成研究2017

    • Author(s)
      前田 充俊・佐藤 誠也・中野啓二・市川 善康
    • Organizer
      日本化学会 中国四国支部大会
    • Related Report
      2017 Research-status Report
  • [Presentation] テルペンの合成研究2017

    • Author(s)
      前田 充俊・佐藤 誠也・市川 善康
    • Organizer
      日本化学会 第97春季年会
    • Related Report
      2017 Research-status Report 2016 Research-status Report
  • [Presentation] (-)-α-サントニンの誘導2016

    • Author(s)
      池田晃章,市川善康
    • Organizer
      2016年日本化学会中国四国支部大会 香川大会
    • Place of Presentation
      香川大学幸町キャンパス
    • Year and Date
      2016-11-05
    • Related Report
      2016 Research-status Report
  • [Presentation] 無保護糖 N-グリコシル化反応によるグリコシルホルムアミドの合成2016

    • Author(s)
      松川旭仁,北森あゆみ,三村利香,前田充俊,冨重蓮華、富田ゆみ子,市川善康
    • Organizer
      2016年日本化学会中国四国支部大会 香川大会
    • Place of Presentation
      香川大学幸町キャンパス
    • Year and Date
      2016-11-05
    • Related Report
      2016 Research-status Report
  • [Presentation] 無保護糖 N-グリコシル化反応によるグリコシルホルムアミドの合成2016

    • Author(s)
      北森 あゆみ・三村 利香・松川 旭仁・市川 善康
    • Organizer
      第35回日本糖質学会年会(高知)
    • Place of Presentation
      高知市文化プラザ かるぽーと
    • Year and Date
      2016-09-01
    • Related Report
      2016 Research-status Report

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

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