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Natural Product Synthesis Based on New Methods for Constructing Quaternary Stereogenic Carbon Atoms

Research Project

Project/Area Number 18H01970
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionHokkaido University

Principal Investigator

TANINO Keiji  北海道大学, 理学研究院, 教授 (40217146)

Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥16,900,000 (Direct Cost: ¥13,000,000、Indirect Cost: ¥3,900,000)
Fiscal Year 2020: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2019: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2018: ¥5,980,000 (Direct Cost: ¥4,600,000、Indirect Cost: ¥1,380,000)
Keywords合成化学 / 四級炭素 / 転位反応 / 天然物合成 / 第四級不斉炭素 / 高次構造天然物 / 全合成
Outline of Final Research Achievements

A new method for stereoselective construction of a quaternary stereogenic carbon atom was developed based on a formal rearrangement reaction of epoxy cyanoalcohols. The utility of the new method was demonstrated through the concise total synthesis of verrucarol, the saponification product of the macrocyclic fungal metabolite verrucarin J.
On the other hand, total synthesis of Hispidospermidin, a natural product possessing a unique caged skeleton, was accomplished based on a two-step transformation of a ketone into a gem-divinyl compound by a rearrangement reaction.

Academic Significance and Societal Importance of the Research Achievements

天然物の全合成研究は、新しい合成手法の開発を促し、有機化学の飛躍的な発展をもたらしてきた。その意義は単に学術面に留まらず、医薬や農薬の創出など社会的な要請にも応えるものである。
本研究では、独自に設計した「エポキシニトリルの形式的転位反応」および「転位反応によるgem-ジビニル化合物の高効率合成」を用いて、従来困難とされてきた第四級不斉炭素の立体選択的かつ効率的な構築法を開発した。また、それら新手法の有用性を、天然物ベルカロールおよびヒスピドスペルミジンの短段階全合成において実証した。

Report

(4 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • Research Products

    (16 results)

All 2021 2020 2019 2018

All Journal Article (13 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 13 results,  Open Access: 4 results) Presentation (3 results) (of which Int'l Joint Research: 2 results,  Invited: 3 results)

  • [Journal Article] Development of a mugineic acid family phytosiderophore analog as an iron fertilizer2021

    • Author(s)
      Motofumi Suzuki, Atsumi Urabe, Sayaka Sasaki, Ryo Tsugawa, Satoshi Nishio, Haruka Mukaiyama, Yoshiko Murata et al
    • Journal Title

      Nature Communications

      Volume: 12 Issue: 1 Pages: 1558-1558

    • DOI

      10.1038/s41467-021-21837-6

    • NAID

      120007141554

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthetic Studies on Cyclocitrinol: Construction of the ABC Ring System Based on Epoxy?Nitrile Cyclization2021

    • Author(s)
      Tanino Keiji、Sato Kazuto
    • Journal Title

      Synlett

      Volume: 32 Issue: 07 Pages: 674-678

    • DOI

      10.1055/a-1334-6100

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hatching stimulation activity of steroidal glycoalkaloids toward the potato cyst nematode, <i>Globodera rostochiensis</i>2020

    • Author(s)
      Shimizu Kosuke、Kushida Atsuhiko、Akiyama Ryota、Lee Hyoung Jae、Okamura Yuya、Masuda Yuki、Sakata Itaru、Tanino Keiji、Matsukida Seiji、Inoue Tsutomu、Sugimoto Yukihiro、Mizutani Masaharu
    • Journal Title

      Plant Biotechnology

      Volume: 37 Issue: 3 Pages: 319-325

    • DOI

      10.5511/plantbiotechnology.20.0516a

    • NAID

      130007907455

    • ISSN
      1342-4580, 1347-6114
    • Year and Date
      2020-09-25
    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] The hatching-stimulation activity of solanoeclepin A toward the eggs of Globodera (Tylenchida: Heteroderidae) species2020

    • Author(s)
      Sakata Itaru、Kushida Atsuhiko、Tanino Keiji
    • Journal Title

      Applied Entomology and Zoology

      Volume: 56 Issue: 1 Pages: 51-57

    • DOI

      10.1007/s13355-020-00707-5

    • NAID

      40022476328

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Formal Total Synthesis of Atropurpuran2020

    • Author(s)
      Suzuki Takahiro、Koyama Takeshi、Nakanishi Kenta、Kobayashi Susumu、Tanino Keiji
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 85 Issue: 15 Pages: 10125-10135

    • DOI

      10.1021/acs.joc.0c01462

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Development of a 1,3a,6a-Triazapentalene Derivative as a Compact and Thiol-specific Fluorescent Labeling Reagent2020

    • Author(s)
      Atsushi Nakayama, Akira Otani, Tsubasa Inokuma, Daisuke Tsuji, Haruka Mukaiyama, Akira Nakayama, Kohji Itoh, Akira Otaka, Keiji Tanino, and Kosuke Namba
    • Journal Title

      Communications Chemistry

      Volume: 3 Issue: 1 Pages: 1-9

    • DOI

      10.1038/s42004-019-0250-0

    • NAID

      120006877882

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Inhibition of Lipid Droplet Formation by Ser/Thr Protein Phosphatase PPM1D Inhibitor, SL-1762019

    • Author(s)
      Rui Kamada, Nozomi Kimura, Fumihiko Yoshimura, Keiji Tanino, and Kazuyasu Sakaguchi
    • Journal Title

      Pros One

      Volume: 14 Issue: 2 Pages: e0212682-e0212682

    • DOI

      10.1371/journal.pone.0212682

    • Related Report
      2019 Annual Research Report 2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Asymmetric Total Synthesis of Laurallene2019

    • Author(s)
      Yoshimura Fumihiko、Okada Taku、Tanino Keiji
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 2 Pages: 559-562

    • DOI

      10.1021/acs.orglett.8b03889

    • Related Report
      2019 Annual Research Report 2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthetic study of andrastins: stereoselective construction of the BCD-ring system2019

    • Author(s)
      Yoshimura Fumihiko、Abe Taiki、Ishioka Yuichi、Tanino Keiji
    • Journal Title

      The Journal of Antibiotics

      Volume: 72 Issue: 6 Pages: 384-388

    • DOI

      10.1038/s41429-018-0136-x

    • NAID

      120006651803

    • Related Report
      2019 Annual Research Report 2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] An Intermolecular [4+3] Cycloaddition Reaction Using 3-Hydroxy-2-pyrone Derivatives with an Oxyallyl Cation2019

    • Author(s)
      Takahiro Suzuki, Takamune Yanagisawa, and Keiji Tanino
    • Journal Title

      Heterocycles

      Volume: 99 Issue: 2 Pages: 848-855

    • DOI

      10.3987/com-18-s(f)79

    • Related Report
      2019 Annual Research Report 2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Substituted Cyclopentenol Derivatives via Intramolecular Addition Reaction of Vinylcopper Species2019

    • Author(s)
      Hideomi Yamaga and Keiji Tanino
    • Journal Title

      Synlett

      Volume: 30 Issue: 02 Pages: 230-234

    • DOI

      10.1055/s-0037-1611366

    • Related Report
      2019 Annual Research Report 2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Total Synthesis of Brasilicardins2018

    • Author(s)
      Yoshimura Fumihiko、Itoh Ryusei、Torizuka Makoto、Mori Genki、Tanino Keiji
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 57 Issue: 52 Pages: 17161-17167

    • DOI

      10.1002/anie.201811403

    • NAID

      120006775546

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Total Synthesis of (-)-Maldoxin, a Common Biosynthetic Ancestor of the Chloropupukeananin Family2018

    • Author(s)
      Takahiro Suzuki, Soichiro Watanabe, Muhammet Uyanik, Kazuaki Ishihara, Susumu Kobayashi, and Keiji Tanino
    • Journal Title

      Org. Lett.

      Volume: 20 Issue: 13 Pages: 3919-3922

    • DOI

      10.1021/acs.orglett.8b01502

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Natural Product Synthesis Based on Cyclization Reactions of Nitriles2019

    • Author(s)
      Keiji Tanino
    • Organizer
      The 8th Japanese-Sino Symposium on Organic Chemistry for Young Scientists
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] シアノ基の特性を活用した天然物合成2019

    • Author(s)
      谷野圭持
    • Organizer
      名古屋大学第111回創薬科学セミナー
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Total Synthesis of Natural Products Based on Cyclization Reactions of Nitriles2019

    • Author(s)
      Keiji Tanino
    • Organizer
      Hokkaido University & Peking University Joint Symposium 2019
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited

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Published: 2018-04-23   Modified: 2022-01-27  

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