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Development of a catalytic method for radical generation at alpha-position of carboxylic acid

Research Project

Project/Area Number 18K14207
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionHokkaido University

Principal Investigator

Shimizu Yohei  北海道大学, 理学研究院, 准教授 (60609816)

Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2019: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Fiscal Year 2018: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Keywordsカルボン酸 / ホウ素触媒 / 光 / ラジカル活性 / ホウ素 / ラジカル / 触媒 / 光酸化還元触媒 / アリル化 / 配位子 / 光触媒
Outline of Final Research Achievements

In this research project, we were able to achieve the following two results: (1) discovery of boron-catalyzed α-allylation of carboxylic acids in combination with visible light irradiation, and (2) development of boron-catalyzed α-amination of carboxylic acids. In the first achievement, we were able to discover a new reactivity of boron catalysis, and it will be the basis for expanding the application to more diverse reaction systems. In the second achievement, we established a method for synthesizing sterically hindered α-amino acids , which is difficult to synthesize by other methods. This method would accelerate the application of unnatural amino acids to various field by supplying order-made amino acids.

Academic Significance and Societal Importance of the Research Achievements

カルボン酸のα位アリル化反応の開発においては、ホウ素触媒と光照射を組み合わせることで、これまでにない反応性を見出すことができたという点で学術的意義が大きい。一方、カルボン酸α位アミノ化反応の開発は、非天然αアミノ酸の簡便な供給方法として利用可能である。非天然アミノ酸は医薬化合物をはじめとして利用価値が高いため、入手容易なカルボン酸から付加価値の高いアミノ酸を合成できるという点で社会的意義があると言える。

Report

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

    (33 results)

All 2021 2020 2019 2018 Other

All Journal Article (7 results) (of which Peer Reviewed: 7 results,  Open Access: 2 results) Presentation (22 results) (of which Int'l Joint Research: 2 results,  Invited: 6 results) Remarks (4 results)

  • [Journal Article] A Stable and Cleavable <i>O</i>-Linked Spacer for Drug Delivery Systems2020

    • Author(s)
      Ito Kei、Tatsumi Toshifumi、Takahashi Kazuki、Shimizu Yohei、Yamatsugu Kenzo、Kanai Motomu
    • Journal Title

      Chemical and Pharmaceutical Bulletin

      Volume: 68 Issue: 3 Pages: 212-215

    • DOI

      10.1248/cpb.c19-00376

    • NAID

      130007804083

    • ISSN
      0009-2363, 1347-5223
    • Year and Date
      2020-03-01
    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Copper-Catalyzed Enantioselective Conjugate Reduction of α,β-Unsaturated Esters with Phenol-Carbene Chiral Ligand2020

    • Author(s)
      Mimura Shohei、Mizushima Sho、Shimizu Yohei、Sawamura Masaya
    • Journal Title

      Beilstein Journal of Organic Chemistry

      Volume: 16 Pages: 537-543

    • DOI

      10.3762/bjoc.16.50

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Copper(I)-Catalyzed Stereodivergent Propargylation of N-Acetyl Mannosamine for Protecting Group Minimal Synthesis of C3-Substituted Sialic Acids2019

    • Author(s)
      Ishizawa Kouhei、Majima Sohei、Wei Xiao-Feng、Mitsunuma Harunobu、Shimizu Yohei、Kanai Motomu
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 84 Issue: 17 Pages: 10615-10628

    • DOI

      10.1021/acs.joc.9b00887

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Boron-Catalyzed α-Amination of Carboxylic Acids2019

    • Author(s)
      Morisawa Takuto、Sawamura Masaya、Shimizu Yohei
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 18 Pages: 7466-7469

    • DOI

      10.1021/acs.orglett.9b02769

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Synthesis of α-Alkylidene-β-Lactams through Copper Catalysis with a Prolinol-Phosphine Chiral Ligand2019

    • Author(s)
      Imai Koji、Takayama Yurie、Murayama Hiroaki、Ohmiya Hirohisa、Shimizu Yohei、Sawamura Masaya
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 6 Pages: 1717-1721

    • DOI

      10.1021/acs.orglett.9b00276

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Catalytic Regio- and Enantioselective Proton Migration from Skipped Enynes to Allenes2019

    • Author(s)
      Wei Xiao-Feng、Wakaki Takayuki、Itoh Taisuke、Li Hong-Liang、Yoshimura Takayoshi、Miyazaki Aya、Oisaki Kounosuke、Hatanaka Miho、Shimizu Yohei、Kanai Motomu
    • Journal Title

      Chem

      Volume: 5 Issue: 3 Pages: 585-599

    • DOI

      10.1016/j.chempr.2018.11.022

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Chemo- and Enantioselective Pd/B Hybrid Catalysis for the Construction of Acyclic Quaternary Carbons: Migratory Allylation of O-Allyl Esters to α-C-Allyl Carboxylic Acids2018

    • Author(s)
      Fujita Taiki、Yamamoto Tomohiro、Morita Yuya、Chen Hongyu、Shimizu Yohei、Kanai Motomu
    • Journal Title

      Journal of the American Chemical Society

      Volume: 140 Issue: 18 Pages: 5899-5903

    • DOI

      10.1021/jacs.8b02783

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Presentation] Chemoselective α-Functionalization of Carboxylic Acids2021

    • Author(s)
      Yohei Shimizu
    • Organizer
      2020 Dalian University of Technology-Overseas Partner Universities Series Online Exchange Conference
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ホウ素触媒を用いた可視光駆動型カルボン酸α位アミノ化反応2021

    • Author(s)
      森沢卓斗・清水洋平・澤村正也
    • Organizer
      日本化学会第101春季年会(2021)
    • Related Report
      2020 Annual Research Report
  • [Presentation] Boron-catalyzed α-Allylation of Carboxylic Acids Driven by Photoirradiation2021

    • Author(s)
      Sun Kai, Masato Ueno, Yohei Shimizu, Masaya Sawamura
    • Organizer
      日本化学会第101春季年会(2021)
    • Related Report
      2020 Annual Research Report
  • [Presentation] キラルプロリノール-ホスフィン-銀触媒を用いたイソシアノ酢酸アミドの不斉アルドール反応2021

    • Author(s)
      酒井聡史・今井 洸児・藤岡 茜・東田皓介・清水 洋平・澤村 正也
    • Organizer
      日本化学会第101春季年会(2021)
    • Related Report
      2020 Annual Research Report
  • [Presentation] Carboxylic acid-selective α-functionalization enabled by boron catalyst2020

    • Author(s)
      Yohei Shimizu
    • Organizer
      The 11th CSE Autumn School & The 8th ALP International Symposium
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] キラルプロリノール-ホスフィン-銀触媒を用いたイソシアノ酢酸アミドの不斉アルドール反応2020

    • Author(s)
      今井洸児、藤岡茜、清水洋平、澤村正也
    • Organizer
      第100回日本化学会春季年会(2020)
    • Related Report
      2019 Research-status Report
  • [Presentation] ホウ素触媒を用いるカルボン酸α位アミノ化反応の開発 Boron-Catalyzed α-Amination of Carboxylic Acids2020

    • Author(s)
      森沢卓斗、清水洋平、澤村正也
    • Organizer
      第100回日本化学会春季年会(2020)
    • Related Report
      2019 Research-status Report
  • [Presentation] ホウ素触媒によるカルボン酸α位アミノ化反応の開発2020

    • Author(s)
      清水洋平、森沢卓斗、澤村正也
    • Organizer
      日本薬学会 第140年会(京都
    • Related Report
      2019 Research-status Report
  • [Presentation] Carboxylic acid-selective enolate formation2019

    • Author(s)
      Yohei Shimizu
    • Organizer
      Hokkaido Summer Symposium 2019 on Catalysis for Organic Synthesis
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] ホウ素触媒と可視光が駆動するカルボン酸α位アリル化反応2019

    • Author(s)
      清水洋平
    • Organizer
      第9回有機分子構築法夏の勉強会
    • Related Report
      2019 Research-status Report
  • [Presentation] ホウ素触媒と可視光が駆動するカルボン酸α位アリル化反応2019

    • Author(s)
      清水洋平、上野雅人、澤村正也
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] キラルプロリノール-ホスフィン-銅触媒によるα-アルキリデン- β-ラクタムの不斉合成2019

    • Author(s)
      今井洸児、高山ゆりえ、村山大明、大宮寛久、清水洋平、澤村正也
    • Organizer
      第36回有機合成化学セミナー
    • Related Report
      2019 Research-status Report
  • [Presentation] Boron Catalyst and Visible Light-Driven α-Allylation of Carboxylic Acids2019

    • Author(s)
      Yohei Shimizu, Masato Ueno, Masaya Sawamura
    • Organizer
      ICCEOCA-14
    • Related Report
      2019 Research-status Report
  • [Presentation] Ir/B Hybrid asymmetric catalysis for stereodivergent construction of α-quaternary-β-tertiary carboxylic acids2019

    • Author(s)
      Hongyu Chen, Shigeru Yamaguchi, Yuya Morita, Yuki Nishioka, Xiangning Zhai, Yohei Shimizu, Harunobu Mitsunuma, Motomu Kanai
    • Organizer
      第12回 有機触媒シンポジウム
    • Related Report
      2019 Research-status Report
  • [Presentation] Boron Catalyst and Visible Light-Driven α-Allylation of Carboxylic Acids2019

    • Author(s)
      Yohei Shimizu, Masato Ueno, Masaya Sawamura
    • Organizer
      2nd ICReDD International Symposium -Toward Interdisciplinary Research Guided by Theory and Calculation-
    • Related Report
      2019 Research-status Report
  • [Presentation] Boron-Catalyzed α-Functionalization of Carboxylic Acids2019

    • Author(s)
      Yohei Shimizu
    • Organizer
      Hokkaido mini-Symposium by Young Generations in Asia
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] 触媒の特性を活かした化学選択的反応の開発2019

    • Author(s)
      清水洋平
    • Organizer
      日本薬学会 第139年会(千葉)
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] Stereodivergent Synthesis of α-Allyl Carboxylic Acids by Boron-Iridium Hybrid Catalysis2019

    • Author(s)
      陳 虹宇, 藤田 大樹, 森田 雄也, 三ツ沼 治信, 清水 洋平, 金井 求
    • Organizer
      日本薬学会 第139年会(千葉)
    • Related Report
      2018 Research-status Report
  • [Presentation] Development of Formal Asymmetric Ireland-Claisen Rearrangements by B/Pd Hybrid Catalysis2018

    • Author(s)
      Yohei Shimizu, Taiki Fujita, Tomohiro Yamamoto, Yuya Morita, Chen Hongyu, Motomu Kanai
    • Organizer
      The 13th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-13
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] 触媒の特性を活かした化学選択的反応の開発2018

    • Author(s)
      清水洋平
    • Organizer
      若手研究者のための有機化学札幌セミナー
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] 銅触媒を用いた無保護糖の立体選択的プロパルギル化を経由する3位置換シアル酸誘導体の短工程合成2018

    • Author(s)
      真島壮平, 石澤公平, 魏暁峰, 三ツ沼治信, 清水洋平, 金井求
    • Organizer
      第35回有機合成化学セミナー
    • Related Report
      2018 Research-status Report
  • [Presentation] ホウ素/パラジウムハイブリッド触媒を用いた化学選択的不斉アリル転位反応の開発2018

    • Author(s)
      藤田大樹, 山本倫広, 森田雄也, 清水洋平, 金井求
    • Organizer
      第35回有機合成化学セミナー
    • Related Report
      2018 Research-status Report
  • [Remarks] 北海道大学大学院理学研究院化学部門 有機金属化学研究室

    • URL

      https://wwwchem.sci.hokudai.ac.jp/~orgmet/index.php?id=644

    • Related Report
      2019 Research-status Report
  • [Remarks] ICReDD

    • URL

      https://www.icredd.hokudai.ac.jp/shimizu-yohei

    • Related Report
      2019 Research-status Report
  • [Remarks] 北海道大学大学院理学研究院

    • URL

      https://www2.sci.hokudai.ac.jp/faculty/researcher/yohei-shimizu

    • Related Report
      2019 Research-status Report
  • [Remarks] 有機金属化学研究室

    • URL

      https://wwwchem.sci.hokudai.ac.jp/~orgmet/

    • Related Report
      2018 Research-status Report

URL: 

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

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