• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Development of novel polyol synthesis using unprotected alcohols

Research Project

Project/Area Number 21K15220
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 47010:Pharmaceutical chemistry and drug development sciences-related
Research InstitutionThe University of Tokyo

Principal Investigator

Harunobu Mitsunuma  東京大学, 大学院薬学系研究科(薬学部), 助教 (20823818)

Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2022: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2021: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
Keywords医薬品合成 / 原子効率 / 短工程 / 保護基フリー / 触媒 / ポリオール / 光レドックス触媒 / HAT触媒 / クロム触媒 / 求核付加反応 / 無保護アルコール / 光触媒 / ラジカル
Outline of Research at the Start

ポリオール骨格は多くの生物活性分子、医薬品、機能性材料に頻出する重要構造である。
この骨格構築に関しては歴史的に多くの手法が開発されてきたが、反応効率、工程数や原子
効率が課題になることが多く理想的な合成法は未だ存在しない。今回、申請者は無保護アル
コールを直接原料とし、アルコールα位で生成した金属種による求核付加反応を行い、ポリ
オール類の網羅的合成法を確立することを目指す。無保護アルコールを原料とすることで廃
棄物を全く出さない単工程での炭素骨格伸長が実現できる。

Outline of Final Research Achievements

The polyol skeleton is a critical structure frequently encountered in numerous bioactive molecules, pharmaceuticals, and functional materials. Historically, various methodologies have been developed for the construction of this skeleton, yet challenges related to reaction efficiency, the number of steps, and atom economy often persist, and an ideal synthetic method has not yet been established. I discovered that using readily accessible simple alkenes as nucleophiles, and employing a consecutive catalytic allylation reaction to aldehydes, which does not require the protection of hydroxyl groups, leads to an efficient synthesis of 1,3-polyols.

Academic Significance and Societal Importance of the Research Achievements

本研究成果では1,3ポリオール合成を無保護にて行う炭素伸長法を開発した。これは今までに前例がなく学術的に価値がある。これにより余計な工程数やごみの排出を抑え、医薬品や生物活性分子の迅速合成が可能になることが予想される。ひいては新規医薬シーズの発見や合成コストの低下による薬価削減につながるものだと考えている。

Report

(4 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Research-status Report
  • 2021 Research-status Report
  • Research Products

    (28 results)

All 2024 2023 2022 2021

All Journal Article (9 results) (of which Peer Reviewed: 9 results,  Open Access: 1 results) Presentation (18 results) (of which Int'l Joint Research: 3 results,  Invited: 9 results) Book (1 results)

  • [Journal Article] Quantitative Assays for Catalytic Photo-Oxygenation of Alzheimer Disease-Related Tau Proteins2023

    • Author(s)
      Umeda Hiroki、Sawazaki Taka、Furuta Masahiro、Suzuki Takanobu、Kawashima Shigehiro A.、Mitsunuma Harunobu、Hori Yukiko、Tomita Taisuke、Sohma Youhei、Kanai Motomu
    • Journal Title

      ACS Chemical Neuroscience

      Volume: 14 Issue: 15 Pages: 2710-2716

    • DOI

      10.1021/acschemneuro.3c00264

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Lewis Acid-Conjugated Pyrene Photoredox Catalyst Promoting the Addition Reaction of α-Silyl Amines with Benzalmalononitriles2022

    • Author(s)
      Katayama Yuri、Mitsunuma Harunobu、Kanai Motomu
    • Journal Title

      Chemical and Pharmaceutical Bulletin

      Volume: 70 Issue: 11 Pages: 765-768

    • DOI

      10.1248/cpb.c22-00526

    • ISSN
      0009-2363, 1347-5223
    • Year and Date
      2022-11-01
    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] Site-Selective α-Alkylation of 1,3-Butanediol Using a Thiophosphoric Acid Hydrogen Atom Transfer Catalyst2022

    • Author(s)
      Nakao Hiroyasu、Mitsunuma Harunobu、Kanai Motomu
    • Journal Title

      Chemical and Pharmaceutical Bulletin

      Volume: 70 Issue: 8 Pages: 540-543

    • DOI

      10.1248/cpb.c22-00299

    • ISSN
      0009-2363, 1347-5223
    • Year and Date
      2022-08-01
    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] A Catalytic Alkylation of Ketones via sp3 C-H Bond Activation2022

    • Author(s)
      Peng Xue、Hirao Yuki、Yabu Shunsuke、Sato Hirofumi、Higashi Masahiro、Akai Takuya、Masaoka Shigeyuki、Mitsunuma Harunobu、Kanai Motomu
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 無し Issue: 10 Pages: 0000-0000

    • DOI

      10.1021/acs.joc.2c00603

    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] Linear‐Selective Allylation of Aldehydes with Simple Alkenes Mediated by Quadruple Hybrid Catalysis2022

    • Author(s)
      Irie Yu、Chen Hongyu、Fuse Hiromu、Mitsunuma Harunobu、Kanai Motomu
    • Journal Title

      Advanced Synthesis & Catalysis

      Volume: 364 Issue: 19 Pages: 3378-3383

    • DOI

      10.1002/adsc.202200704

    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] Titanium(IV) Chloride-Catalyzed Photoalkylation via C(sp3)-H Bond Activation of Alkanes2022

    • Author(s)
      Yamane Mina、Kanzaki Yamato、Mitsunuma Harunobu、Kanai Motomu
    • Journal Title

      Organic Letters

      Volume: 24 Issue: 7 Pages: 1486-1490

    • DOI

      10.1021/acs.orglett.2c00138

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Identification of a Self-Photosensitizing Hydrogen Atom Transfer Organocatalyst System2022

    • Author(s)
      Fuse Hiromu、Irie Yu、Fuki Masaaki、Kobori Yasuhiro、Kato Kosaku、Yamakata Akira、Higashi Masahiro、Mitsunuma Harunobu、Kanai Motomu
    • Journal Title

      Journal of the American Chemical Society

      Volume: 144 Issue: 14 Pages: 6566-6574

    • DOI

      10.1021/jacs.2c01705

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Recent Progress in Chromium-Mediated Carbonyl Addition Reactions2021

    • Author(s)
      Mitsunuma Harunobu、Kanai Motomu、Katayama Yuri
    • Journal Title

      Synthesis

      Volume: 54 Issue: 07 Pages: 1684-1694

    • DOI

      10.1055/a-1696-6429

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Siloxy Esters as Traceless Activators of Carboxylic Acids: Boron‐Catalyzed Chemoselective Asymmetric Aldol Reaction**2021

    • Author(s)
      Fujita Taiki、Yamane Mina、Sameera W. M. C.、Mitsunuma Harunobu、Kanai Motomu
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Issue: 46 Pages: 24598-24604

    • DOI

      10.1002/anie.202109788

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Presentation] 不活性アルケンを用いたケトンの触媒的アリル化反応2024

    • Author(s)
      有井優,陳 虹宇,三ツ沼治信,金井求
    • Organizer
      日本化学会 第104春季年会
    • Related Report
      2023 Annual Research Report
  • [Presentation] Identification of a Self-Photosensitizing Hydrogen Atom Transfer Organocatalyst System2023

    • Author(s)
      H. Mitsunuma, H. Fuse, Y. Irie, M. Fuki, Y. Kobori, K. Kato, A. Yamakata, M. Higashi, M. Kanai
    • Organizer
      243rd Meeting of The Electrochemical Society
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 電荷移動錯体を利用した光駆動型有機水素原子移動触媒の開発2023

    • Author(s)
      三ツ沼 治信・布施 拡・入江 優・婦木 正明・小堀 康博・ 加藤 康作・山方 啓・東 雅大・金井 求
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2023 Annual Research Report 2022 Research-status Report
    • Invited
  • [Presentation] Grignard反応の革新を目指して2023

    • Author(s)
      三ツ沼 治信
    • Organizer
      有機金属化学若手の会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] Grignard反応の革新を目指して2023

    • Author(s)
      三ツ沼 治信
    • Organizer
      神戸大学有機反応化学研究会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] Development of Catalytic Asymmetric Allylation of Ketones Using Unactivated Alkenes2023

    • Author(s)
      有井優,陳 虹宇,三ツ沼治信,金井求
    • Organizer
      第39回 有機合成化学セミナー
    • Related Report
      2023 Annual Research Report
  • [Presentation] 不活性アルケンを用いた四成分触媒系によるアルデヒドのlinear選択的アリル化2023

    • Author(s)
      入江 優 、陳虹宇、布施 拡 、三ツ沼 治信 、金井 求
    • Organizer
      日本薬学会第143年会
    • Related Report
      2022 Research-status Report
  • [Presentation] ルイス酸共役型ピレン光レドックス触媒による α-シリルアミンのラジカル付加反応2023

    • Author(s)
      片山 友里、三ツ沼 治信、金井 求
    • Organizer
      日本薬学会第143年会
    • Related Report
      2022 Research-status Report
  • [Presentation] Titanium-Catalyzed Intermolecular Radical Addition to Ketones via sp3 C-H Bond Activation2022

    • Author(s)
      Harunobu Mitsunuma, Xue Peng, Yuki Hirao, Shunsuke Yabu, Hirofumi Sato, Masahiro Higashi, Motomu Kanai
    • Organizer
      241st ECS meeting
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 電荷移動錯体を利用した光駆動型有機水素原子移動触媒の開発2022

    • Author(s)
      三ツ沼 治信・布施 拡・入江 優・婦木 正明・小堀 康博・ 加藤 康作・山方 啓・東 雅大・金井 求
    • Organizer
      2022年光化学討論会
    • Related Report
      2022 Research-status Report
    • Invited
  • [Presentation] Titanium-Catalyzed Intermolecular Radical Addition to Ketones via sp3 C-H Bond Activation2022

    • Author(s)
      Xue Peng, Yuki Hirao, Shunsuke Yabu, Hirofumi Sato, Masahiro Higashi, Harunobu Mitsunuma, Motomu Kanai
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2022 Research-status Report
  • [Presentation] TiCl4をHAT光触媒とするアルカンC(sp3)-H活性化反応2022

    • Author(s)
      山根三奈、神崎倭、三ツ沼治信、金井求
    • Organizer
      日本薬学会第143回年会
    • Related Report
      2022 Research-status Report
  • [Presentation] Linear-Selective Allylation of Aldehydes with Simple Alkenes Mediated by Quadruple Hybrid Catalysis2022

    • Author(s)
      Yu Irie, Hongyu Chen, Hiromu Fuse, Harunobu Mitsunuma, Motomu Kanai
    • Organizer
      有機合成セミナー
    • Related Report
      2022 Research-status Report
  • [Presentation] 不活性アルケンを用いたアルデヒドのlinear選択的アリル化2022

    • Author(s)
      入江 優 、布施 拡 、三ツ沼 治信 、金井 求
    • Organizer
      日本薬学会第142年会
    • Related Report
      2022 Research-status Report
  • [Presentation] Catalytic Allylation of Aldehydes Using Feedstock Alkenes2021

    • Author(s)
      Mitsunuma Harunobu, Shun Tanabe, Motomu Kanai
    • Organizer
      The 11th International Conference on Flexible and Printed Electronics
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 石油資源アルケンを用いたアルデヒドの触媒的アリル化2021

    • Author(s)
      三ツ沼 治信, 田辺 駿, 金井 求
    • Organizer
      2021年光化学討論会
    • Related Report
      2021 Research-status Report
    • Invited
  • [Presentation] 光増感分子触媒を利用したsp3C-H変換反応の開発2021

    • Author(s)
      三ツ沼治信
    • Organizer
      第15回物性科学領域横断研究会
    • Related Report
      2021 Research-status Report
  • [Presentation] 光増感分子触媒を利用したC-H 変換反応の開発2021

    • Author(s)
      三ツ沼治信
    • Organizer
      機能性色素部会第104 回例会
    • Related Report
      2021 Research-status Report
    • Invited
  • [Book] 有機光反応の化学2022

    • Author(s)
      三ツ沼治信、金井求
    • Total Pages
      216
    • Publisher
      化学同人
    • ISBN
      9784759814033
    • Related Report
      2021 Research-status Report

URL: 

Published: 2021-04-28   Modified: 2025-01-30  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi