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Total Synthesis of (+)-ascospiroketals A,B and Determination of there Absolute Configurations

Research Project

Project/Area Number 26460028
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Chemical pharmacy
Research InstitutionTokushima Bunri University

Principal Investigator

Esumi Tomoyuki  徳島文理大学, 薬学部, 准教授 (50315264)

Project Period (FY) 2014-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥5,200,000 (Direct Cost: ¥4,000,000、Indirect Cost: ¥1,200,000)
Fiscal Year 2016: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000)
Fiscal Year 2015: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2014: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
Keywordsascospiroketal / 1,4-addition reaction / asymmetric aldol / diastereo selective / ganmma-lactone / beta-lactone / decarboxylation / organic synthesis / asymmetric / synthesis / natural product / polyketide / 1,4-addition / aldol reaction / 結核 / 不斉1,4-付加 / 不斉アルドール / β-ラクトン / 連続不斉中心 / 不斉四級炭素 / 天然物合成 / ascospiroketals / tetraalkylated / all-carbon / quaternary center
Outline of Final Research Achievements

The synthesis of (+)-ascospiroketal B commenced from 2-propyn-1-ol, namely, Negishi iodomethylation of 2-propyn-1-ol followed by protection of hydroxy group by TBDPS and coupling reaction with (S)-2-phenyloxazolidinone accompanied insertion of CO catalyzed by Pd(PPh3)4 afforded 1. Then 1 was treated with vinyl copper reagent and converted to 2 in high diastereoselectivity. The aldol reaction of 2 accompanied by removal of oxazolidinone moiety to form b-lactone ring gave β-lactone 3 as a single isomer. Methylation of 3 with MeLi followed by ozonolysis and PDC oxidation produced γ-lactone 5 in good yields. Although Bayer-Viliger oxidation of 5 with usual reagent such as mCPBA did not proceeded due to the steric strain around methylketone.

Report

(4 results)
  • 2016 Annual Research Report   Final Research Report ( PDF )
  • 2015 Research-status Report
  • 2014 Research-status Report
  • Research Products

    (12 results)

All 2016 2015 2014

All Journal Article (5 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 4 results,  Open Access: 4 results,  Acknowledgement Compliant: 4 results) Presentation (7 results) (of which Int'l Joint Research: 5 results)

  • [Journal Article] Bakuchiol Is a Phenolic Isoprenoid with Novel Enantiomer-​selective Anti-​influenza A Virus Activity Involving Nrf2 Activation2015

    • Author(s)
      Shoji, Masaki; Arakaki, Yumie; Esumi, Tomoyuki; Kohnomi, Shuntaro; Yamamoto, Chihiro; Suzuki, Yutaka; Takahashi, Etsuhisa; Konishi, Shiro; Kido, Hiroshi; Kuzuhara, Takashi
    • Journal Title

      Journal of Biological Chemistry

      Volume: 290 Issue: 46 Pages: 28001-28017

    • DOI

      10.1074/jbc.m115.669465

    • NAID

      120006959751

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Synthetic studies of neurite outgrowth-​promoting neovibsanins2015

    • Author(s)
      Imagawa, Hiroshi; Esumi, Tomoyuki; Fukuyama, Yoshiyasu
    • Journal Title

      Yuki Gosei Kagaku Kyokaishi

      Volume: 73 Pages: 902-910

    • DOI

      10.1016/b978-0-444-63430-6.00002-3

    • NAID

      130005104061

    • Related Report
      2015 Research-status Report
    • Acknowledgement Compliant
  • [Journal Article] Systematic Asymmetric Synthesis of All Diastereomers of (-)-Talaumidin and Their Neurotrophic Activity.2015

    • Author(s)
      Harada, K.; Kubo, M.; Horiuchi, H.; Ishii, A.; Esumi, T.; Hioki, H.; Fukuyama, Y.
    • Journal Title

      J. Org. Chem.

      Volume: 80 Issue: 14 Pages: 7076-7088

    • DOI

      10.1021/acs.joc.5b00945

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Chemical diversity of vibsane-type diterpenoids and neurotrophic activity and synthesis of neovibsanin. Kubo, M.; Esumi, T.; Imagawa, H.; Fukuyama, Y. Studies in Natural Products chemistry 2014, 43, 41-78. ② Seed dormancy breaking diterpenoids from the liverwort Plagiochila sciophila and their differentiation inducing activity in human promyelocytic leukemia HL-60 cells.2014

    • Author(s)
      Kenmoku, H.; Tada, H.; Oogushi, M.; Esumi, T.; Takahashi, H.; Noji, H.; Sassa, M.; Toyota, M.; Asakawa, Y.
    • Journal Title

      Natural Product Communications

      Volume: 7 Issue: 7 Pages: 915-920

    • DOI

      10.3987/rev-10-671

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Chemical diversity of vibsane-type diterpenoids and neurotrophic activity and synthesis of neovibsanin.2014

    • Author(s)
      Kubo, M.; Esumi, T.; Imagawa, H.; Fukuyama, Y.
    • Journal Title

      Studies in Natural Products chemistry

      Volume: 43 Pages: 41-78

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Presentation] Synthesis of Bakuchiol Derivatives and their Anti-Influenza activity.2016

    • Author(s)
      Esumi, T.; Watanabe, M.; Shoji, M.; Kuzuhara, T.
    • Organizer
      French-Japanese Synposium on Medicinal and Fine Chemistry (FJS2016)
    • Place of Presentation
      Tokyo
    • Year and Date
      2016-05-15
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 神経栄養因子様活性天然物,ネオビブサニン類のエナンチオ選択的合成研究2016

    • Author(s)
      新居建生
    • Organizer
      日本薬学会第136年会
    • Place of Presentation
      神奈川県横浜市
    • Year and Date
      2016-03-26
    • Related Report
      2015 Research-status Report
  • [Presentation] ビオチン標識化バクチオール誘導体の合成と抗インフルエンザウイルス活性評価2016

    • Author(s)
      渡辺珠汎
    • Organizer
      日本薬学会第136年会
    • Place of Presentation
      神奈川県横浜市
    • Year and Date
      2016-03-26
    • Related Report
      2015 Research-status Report
  • [Presentation] Enantioselective synthetic study of (+)-neovibsanins A and B2015

    • Author(s)
      江角朋之
    • Organizer
      Inaugural Symposium of the Phytochemical Society of Asia 2015
    • Place of Presentation
      Tokushima, Japan
    • Year and Date
      2015-08-30
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Evalution of talaumidin derivatives on neurite-outgrowth in NGF-differentisted PC12 cells2015

    • Author(s)
      座波
    • Organizer
      Inaugural Symposium of the Phytochemical Society of Asia 2015
    • Place of Presentation
      Tokushima, Japan
    • Year and Date
      2015-08-30
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Bakuchiol, a phenolic isoprenoid, has enantiomer-selective ant-influenza A.2015

    • Author(s)
      庄司正樹
    • Organizer
      Inaugural Symposium of the Phytochemical Society of Asia 2015
    • Place of Presentation
      Tokushima, Japan
    • Year and Date
      2015-08-30
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Enantioselective Synthetic Study of (+)-Neovibsanins A and B2015

    • Author(s)
      江角朋之
    • Organizer
      24th International Symposium: Synthesis in Organic Chemistry
    • Place of Presentation
      Cambridge, UK
    • Year and Date
      2015-07-20
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research

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Published: 2014-04-04   Modified: 2018-03-22  

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