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Highly enantioselective catalysis enabled by breaking away from classical chiral scaffolds

Research Project

Project/Area Number 19H02710
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 InstitutionChiba University

Principal Investigator

Hashimoto Takuya  千葉大学, 大学院理学研究院, 特任准教授 (20437198)

Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥17,420,000 (Direct Cost: ¥13,400,000、Indirect Cost: ¥4,020,000)
Fiscal Year 2021: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2020: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2019: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Keywords触媒的不斉合成 / 不斉配位子
Outline of Research at the Start

触媒的不斉合成とは右手と左手の関係にある分子の片方のみを効率的に合成する手法である。この方法は数十年にわたり日本の得意とする研究分野であり、野依不斉水素化をはじめ多くの重要な研究が日本の研究者によって実現されてきた。しかしながら、この分野においても中国をはじめとする国々の台頭が著しい。本研究では分子デザインを基盤とする新たな触媒的不斉合成法を確立することで、同分野での新たな国際競争力の獲得を目指す。

Outline of Final Research Achievements

In this study, we have developed various catalytic asymmetric transformations using non-classical chiral building blocks, mainly indanols. As a result, we succeeded in synthesizing chiral iodine catalysts, chiral selenium catalysts, and chiral phosphorus ligands with indanols. Furthermore, we found that the synthesized asymmetric catalysts and ligands can achieve unprecedentedly high enantioselectivity in existing asymmetric reactions and originally developed asymmetric reactions.
In the process, we have also succeeded in creating new reactions in which racemic compounds were obtained with classical chiral ligands, and further research development is expected in the future.

Academic Significance and Societal Importance of the Research Achievements

触媒的不斉合成は医薬品をはじめとする光学活性有機化合物を合成する際に必須となる有機合成手法である。しかしながらその中心となる不斉触媒の構造は、アミノ酸やビナフチル基のような「古典的なキラルビルディングブロック」を取り入れたものがほとんどであり、効率的に合成できる光学活性有機化合物の多様性を担保できない状況にあった。本研究においてはこれまで不斉触媒に取り入れられたことのない「非古典的なキラルビルディングブロック」を導入した新規不斉触媒を創出し、各種反応系に適用することで、この問題の解決を図った。

Report

(4 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • Research Products

    (12 results)

All 2022 2021 2020 2019 Other

All Journal Article (5 results) (of which Peer Reviewed: 4 results) Presentation (5 results) (of which Invited: 2 results) Remarks (1 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] An <i>N</i>-Fluorinated Imide for Practical Catalytic Imidations2022

    • Author(s)
      Oe Yuno、Yoshida Ryuhei、Tanaka Airi、Adachi Akiya、Ishibashi Yuichiro、Okazoe Takashi、Aikawa Kohsuke、Hashimoto Takuya
    • Journal Title

      Journal of the American Chemical Society

      Volume: 144 Issue: 5 Pages: 2107-2113

    • DOI

      10.1021/jacs.1c13569

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Organoiodine-Catalyzed Enantioselective Intermolecular Oxyamination of Alkenes2021

    • Author(s)
      Wata Chisato、Hashimoto Takuya
    • Journal Title

      Journal of the American Chemical Society

      Volume: 143 Issue: 4 Pages: 1745-1751

    • DOI

      10.1021/jacs.0c11440

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Organoiodine-Catalyzed Enantioselective Intramolecular Oxyaminations of Alkenes with N-(Fluorosulfonyl)carbamate2021

    • Author(s)
      Wata Chisato、Hashimoto Takuya
    • Journal Title

      Synthesis

      Volume: - Issue: 15 Pages: 2594-2601

    • DOI

      10.1055/s-0037-1610768

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Hydrative para-Dearomatization of Sulfonanilides by an Indanol-based Chiral Organoiodine Catalyst2021

    • Author(s)
      Shimazaki Yuto、Wata Chisato、Hashimoto Takuya、Maruoka Keiji
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: -

    • Related Report
      2020 Annual Research Report
  • [Journal Article] Scalable Synthesis of a Chiral Selenium π-Acid Catalyst and Its Use in Enantioselective Iminolactonization of β,γ-Unsaturated Amides2019

    • Author(s)
      Y. Otsuka, Y. Shimazaki, H. Nagaoka, K. Maruoka, and T. Hashimoto
    • Journal Title

      Synlett

      Volume: 30 Issue: 14 Pages: 1679-1682

    • DOI

      10.1055/s-0039-1690109

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Presentation] 基質デザインによる有機触媒の機能拡張2021

    • Author(s)
      橋本卓也
    • Organizer
      第14回 有機触媒シンポジウム
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] まだまだある、つくる技術2021

    • Author(s)
      橋本卓也
    • Organizer
      CSJ化学フェスタ
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] キラル有機ヨウ素触媒によるアルケンの分子間不斉アミノオキシ化反応の開発2020

    • Author(s)
      綿 智理、橋本 卓也
    • Organizer
      第80回関東支部シンポジウム
    • Related Report
      2020 Annual Research Report
  • [Presentation] 3価の有機ヨウ素試薬を用いたアルケンの分子間syn-アミノオキシ化反応2020

    • Author(s)
      綿智理、橋本卓也
    • Organizer
      日本化学会第100春季年会2020
    • Related Report
      2019 Annual Research Report
  • [Presentation] セレン触媒によるエナンチオ選択的アリル位アミノ化反応2020

    • Author(s)
      大塚祐太、橋本卓也
    • Organizer
      日本化学会第100春季年会2020
    • Related Report
      2019 Annual Research Report
  • [Remarks]

    • URL

      https://www.chiba-u.jp/general/publicity/press/files/2020/20210127iodine.pdf

    • Related Report
      2020 Annual Research Report
  • [Patent(Industrial Property Rights)] アミノ化剤及びアミノ化合物の製造方法2019

    • Inventor(s)
      岡添隆、石橋雄一郎、野崎京子、相川光介、橋本卓也
    • Industrial Property Rights Holder
      岡添隆、石橋雄一郎、野崎京子、相川光介、橋本卓也
    • Industrial Property Rights Type
      特許
    • Filing Date
      2019
    • Related Report
      2019 Annual Research Report

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Published: 2019-04-18   Modified: 2023-01-30  

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