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

A novel approach to chirality control in the synthesis of organofluorine compounds

Research Project

Project/Area Number 16H05077
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionUniversity of Shizuoka

Principal Investigator

Hamashima Yoshitaka  静岡県立大学, 薬学部, 教授 (40333900)

Research Collaborator Egami hiromichi  
Kawato yuji  
Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥18,200,000 (Direct Cost: ¥14,000,000、Indirect Cost: ¥4,200,000)
Fiscal Year 2018: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2017: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2016: ¥9,360,000 (Direct Cost: ¥7,200,000、Indirect Cost: ¥2,160,000)
Keywords不斉合成 / フッ素化学 / 相間移動触媒 / イオン対 / 水素結合 / アルケン / 二官能基化 / 医薬化学 / 有機分子触媒 / フッ素化 / C-H活性化 / C-H結合変換 / フッ素 / 有機化学 / 薬学
Outline of Final Research Achievements

We have succeeded in creating a novel dianionic phase-transfer catalyst to bring strongly electrophilic dicationic fluorinating reagent, Selectfluor to the organic phase, and thus spontaneous racemic reaction is minimized to achieve chirality control of fluorofunctionalization of alkenes. Various allylic amides underwent fluorocyclization in a highly stereoselectivie manner to give drug-like heterocyclic compounds. Additionally, we developed direct Csp3-H fluorination of benzylic and aliphatic substrates under photo-irradiation.

Academic Significance and Societal Importance of the Research Achievements

全元素中最大の電気陰性度を示すフッ素は、創薬科学や機能性物質の研究において非常に関心の高い元素であり、選択的なフッ素化合物合成法の開発は有用である。生体内がキラル環境であることを考慮するとフッ素化におけるキラリティー制御は重要な課題であり、これまでにない手法を見出した本研究の学術的意義は高い。
得られる生成物はそのものがドラッグライクな構造を有しており、またフッ素置換されたアミノアルコール等価体であるため生物活性化合物の部分構造としても有用性が高いため、本法は創薬化学研究における有用なツールに発展すると期待される。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • Research Products

    (46 results)

All 2019 2018 2017 2016 Other

All Journal Article (6 results) (of which Peer Reviewed: 6 results) Presentation (37 results) (of which Int'l Joint Research: 12 results,  Invited: 4 results) Remarks (3 results)

  • [Journal Article] Asymmetric Fluorination of Cyclic Tetrasubstituted Alkenes with a Pendant Amide Groups under Dianionic Phase-Transfer Catalysis2018

    • Author(s)
      Tomoki Niwa, Kiyoshi Ujiie, Hitomi Sato, Hiromichi Egami, Yoshitaka Hamashima
    • Journal Title

      Chemical and Pharmaceutical Bulletin

      Volume: 66 Issue: 10 Pages: 920-922

    • DOI

      10.1248/cpb.c18-00551

    • NAID

      130007491878

    • ISSN
      0009-2363, 1347-5223
    • Year and Date
      2018-10-01
    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Simple Photo-Induced Trifluoromehtylation of Aromatic Rings2018

    • Author(s)
      Hiromichi Egami, Yuta Ito, Takafumi Ide, Shuya Masuda, Yoshitaka Hamashima
    • Journal Title

      Synthesis

      Volume: 50 Issue: 15 Pages: 2948-2953

    • DOI

      10.1055/s-0037-1609759

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Regio- and chemoselective Csp3-H arylation of benzylamines by single electron transfer/hydrogen atom transfer synergistic catalysis2018

    • Author(s)
      Takafumi Ide, Joshua P. Barham, Masashi Fujita, Yuji Kawato, Hiromichi Egami, Yoshitaka Hamashima
    • Journal Title

      Chem. Sci.

      Volume: 9 Issue: 44 Pages: 8453-8460

    • DOI

      10.1039/c8sc02965b

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Photofluorination of Aliphatic C-H Bonds Promoted by the Phthalimide Group2018

    • Author(s)
      Hiromichi Egami, Shuya Masuda, Yuji Kawato, Yoshitaka Hamashima
    • Journal Title

      Organic Letters

      Volume: 20 Issue: 5 Pages: 1367-1370

    • DOI

      10.1021/acs.orglett.8b00133

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Dianionic Phase-Transfer Catalyst for Asymmetric Fluorocyclization2018

    • Author(s)
      Hiromichi Egami, Tomoki Niwa, Hitomi Sato, Ryo Hotta, Taiki Rouno, Yuji Kawato, Yoshitaka Hamashima
    • Journal Title

      Journal of the American Chemical Society

      Volume: 140 Issue: 8 Pages: 2785-2788

    • DOI

      10.1021/jacs.7b13690

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Benzylic C-H Trifluoromethylation via Photoenol2017

    • Author(s)
      Ide Takafumi、Masuda Shuya、Kawato Yuji、Egami Hiromichi、Hamashima Yoshitaka
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 17 Pages: 4452-4455

    • DOI

      10.1021/acs.orglett.7b01971

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Presentation] フタルイミドを利用した光C-Hフッ素化反応2019

    • Author(s)
      江上寛通、増田柊也、川戸勇士、濱島義隆
    • Organizer
      日本薬学会第139年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] チオ安息香酸が触媒するベンジルアミン類の選択的C-Hアリール化反応2019

    • Author(s)
      小林 史尚、藤田 将司、井出 貴文、江上 寛通、濱島 義隆
    • Organizer
      日本薬学会第139年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 光照射による芳香族化合物のトリフルオロメチル化反応2019

    • Author(s)
      伊藤優太、井出貴文、増田柊也、江上寛通、濱島義隆
    • Organizer
      日本薬学会第139年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Asymmetric Dearomative Fluorination with Novel Phase-transfer Catalysts2019

    • Author(s)
      Ryo Hotta, Taiki Rouno, Tomoki Niwa, Hiromichi Egami, Yoshitaka Hamashima
    • Organizer
      日本化学会第99年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Dianionic phase-transfer catalyst for asymmetric fluorofunctionalization2019

    • Author(s)
      Tomoki Niwa, Hitomi Sato, Ryo Hotta, Taiki Rouno, Yuji Kawato, Hiromichi Egami, Yoshitaka Hamashima
    • Organizer
      日本化学会第99年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 光照射による芳香族化合物のトリフルオロメチル化反応2018

    • Author(s)
      伊藤優太、井出貴文、増田柊也、江上寛通、濱島義隆
    • Organizer
      第64回日本薬学会東海支部総会・大会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 光照射による芳香族化合物のトリフルオロメチル化反応2018

    • Author(s)
      伊藤優太、井出貴文、増田柊也、江上寛通、濱島義隆
    • Organizer
      第49回中部化学関係学協会支部連合秋季大会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 光レドックス触媒とチオ安息香酸の協奏的触媒系によるベンジルアミンの酸化的ホモカップリング反応の開発2018

    • Author(s)
      藤田将司、井出貴文、小林史尚、江上寛通、濱島義隆
    • Organizer
      第49回中部化学関係学協会支部連合秋季大会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 環状四置換アルケンに対する不斉フルオロ脱プロトン化反応2018

    • Author(s)
      丹羽智紀、氏家清、佐藤瞳、江上寛通、濱島義隆
    • Organizer
      日本病院薬剤師会東海ブロック・日本薬学会東海支部合同学術大会
    • Related Report
      2018 Annual Research Report
  • [Presentation] ナフトール類の脱芳香環化型不斉フッ素化反応2018

    • Author(s)
      蝋野大輝、増田航佑、丹羽智紀、江上寛通、濱島義隆
    • Organizer
      日本病院薬剤師会東海ブロック・日本薬学会東海支部合同学術大会
    • Related Report
      2018 Annual Research Report
  • [Presentation] フタルイミドを利用した光CーHフッ素化反応2018

    • Author(s)
      江上寛通、増田柊也、川戸勇士、濱島義隆
    • Organizer
      第44回反応と合成の進歩シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] ジアニオン型相間移動触媒を用いた不斉フッ素官能基化反応の開発2018

    • Author(s)
      丹羽智紀、佐藤瞳、氏家清、川戸勇士、江上寛通、濱島義隆
    • Organizer
      第44回反応と合成の進歩シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] 光レドックス触媒とHAT触媒の協奏的触媒系によるアルキルアミン類の選択的C-H変換反応の開発2018

    • Author(s)
      藤田将司、井出貴文、小林史尚、江上寛通、濱島義隆
    • Organizer
      第114回有機合成シンポジウム2018年
    • Related Report
      2018 Annual Research Report
  • [Presentation] Dianionic Phase-Transfer Catalyst for Asymmetric Fluorocyclization2018

    • Author(s)
      Tomoki Niwa, Hitomi Sato, Ryo Hotta, Taiki Rouno, Yuji Kawato, Hiromichi Egami, Yoshitaka Hamashima
    • Organizer
      IKCOC-14
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Regio- and Chemoselective Csp3-H Transformation of Benzylamines by Single Electron Transfer/Hydrogen Atom Transfer Synergistic Catalysis2018

    • Author(s)
      Masashi Fujita, Takafumi Ide, Fumihisa Kobayashi, Hiromichi Egami, Yoshitaka Hamashima
    • Organizer
      IKCOC-14
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] インドール誘導体の脱芳香環化型不斉フッ素化反応2018

    • Author(s)
      蝋野大輝、堀田亮、丹羽智紀、江上寛通、濱島義隆
    • Organizer
      第11回有機触媒シンポジウム
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Asymmetric Halo-functionalization of Alkenes with Novel Organocatalysts2018

    • Author(s)
      Yoshitaka Hamashima
    • Organizer
      International Symposium of Soft Molecular Activation Research Center
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Asymmetric Fluorination with Dianionic Phase Transfer Catalysts2018

    • Author(s)
      Yoshitaka Hamashima
    • Organizer
      The 13th International Conference on Cutting-Edge Organic Chemistry in Asia
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] フタルイミドを利用した光C-Hフッ素化反応2018

    • Author(s)
      江上 寛通、増田 柊也、川戸 勇士、濱島 義隆
    • Organizer
      日本化学会第98会春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] ジアニオン型相間移動触媒を用いた アリルアミド類の不斉ハロ環化反応の開発2018

    • Author(s)
      丹羽智紀、佐藤瞳、堀田亮、蝋野大輝、川戸勇士、江上寛通、濱島義隆
    • Organizer
      日本薬学会第138年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 新規相間移動触媒を用いたオレフィン類の不斉フッ素官能基化反応の開発2017

    • Author(s)
      丹羽智紀、佐藤瞳、堀田 亮、川戸勇士、江上寛通、濱島義隆
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應大学日吉キャンパス
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] ジアニオン型相間移動触媒を用いたインドール誘導体の不斉フッ素環化反応2017

    • Author(s)
      堀田亮、丹羽智紀、川戸勇士、江上寛通、濱島義隆
    • Organizer
      第63回日本薬学会東海支部総会・大会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Design and Synthesis of Chiral Carboxylic Acids and Application to Asymmetric Fluorocyclization2017

    • Author(s)
      Tomoki Niwa, Hitomi Sato, Ryo Hotta, Yuji Kawato, Hiromichi Egami, Yoshitaka Hamashima
    • Organizer
      29th International Symposium on Chirality (Chirality 2017)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Asymmetric Fluorocyclization with Newly Designed Phase Transfer Catalyst2017

    • Author(s)
      Hiromichi Egami, Tomoki Niwa, Hitomi Sato, Ryo Hotta, Yuji Kawato, Yoshitaka Hamashima
    • Organizer
      29th International Symposium on Chirality (Chirality 2017)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ベンゾフェノン誘導体のベンジル位C(sp3)-Hトリフルオロメチル化反応の開発2017

    • Author(s)
      増田柊也、井出貴文、川戸勇士、江上寛通、濱島義隆
    • Organizer
      第7回フッ素化学若手の会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Benzylic C-H Trifluoromethylations2017

    • Author(s)
      Takafumi Ide, Syuya Masuda, Yuji Kawato, Hiromichi Egami, Yoshitaka Hamashima
    • Organizer
      HALCHEM Ⅷ at INUYAMA 2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Design and synthesis of chiral carboxylic acid and application to asymmetric fluorocyclization2017

    • Author(s)
      Tomoki Niwa, Ryou Hotta, Yuji Kawato, Hiromichi Egami, Yoshitaka Hamashima
    • Organizer
      HALCHEM Ⅷ at INUYAMA 2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Phthalimide for Photofluorination of Csp3-H Bond2017

    • Author(s)
      Hiromichi Egami, Shuya Masuda, Yuji Kawato, Yoshitaka Hamashima
    • Organizer
      HALCHEM Ⅷ at INUYAMA 2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ベンジル位C(sp3)-Hトリフルオロメチル化反応の開発2017

    • Author(s)
      井出貴文、増田柊也、川戸勇士、江上寛通、濱島義隆
    • Organizer
      第43回反応と合成の進歩シンポジウム
    • Related Report
      2017 Annual Research Report
  • [Presentation] 新規相間移動触媒を用いる不斉フルオロ環化反応2017

    • Author(s)
      江上寛通、丹羽智紀、佐藤瞳、堀田亮、川戸勇士、濱島義隆
    • Organizer
      第43回反応と合成の進歩シンポジウム
    • Related Report
      2017 Annual Research Report
  • [Presentation] ジアニオン型相間移動触媒を用いたアリルアミド類の不斉フルオロ環化反応の開発2017

    • Author(s)
      丹羽智紀、佐藤瞳、堀田亮、川戸勇士、江上寛通、濱島義隆
    • Organizer
      第48回中部化学関係学協会支部連合秋季大会
    • Related Report
      2017 Annual Research Report
  • [Presentation] フタルイミドを利用した光C-Hフッ素化反応の開発2017

    • Author(s)
      増田柊也、川戸勇士、江上寛通、濱島義隆
    • Organizer
      第48回中部化学関係学協会支部連合秋季大会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Asymmetric Fluorination of Alkenes with Novel Carboxylate Catalysts2017

    • Author(s)
      Yoshitaka Hamashima
    • Organizer
      International Symposium of Pure and Applied Chemistry
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Asymmetric Fluorination of Alkenes with Novel Carboxylate Catalysts2017

    • Author(s)
      Yoshitaka Hamashima
    • Organizer
      HALCHEM Ⅷ at INUYAMA 2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ベンジル位C-Hトリフルオロメチル化反応の開発2016

    • Author(s)
      井出貴文、江上寛通、川戸勇士、濱島義隆
    • Organizer
      第6回CSJ化学フェスタ
    • Place of Presentation
      船堀
    • Year and Date
      2016-11-14
    • Related Report
      2016 Annual Research Report
  • [Presentation] ベンジル位Csp3-Hトリフルオロメチル化反応2016

    • Author(s)
      井出貴文、増田柊也、川戸勇士、江上寛通、濱島義隆
    • Organizer
      フルオラス科学研究会第9回シンポジウム
    • Place of Presentation
      名古屋大学
    • Year and Date
      2016-10-07
    • Related Report
      2016 Annual Research Report
  • [Presentation] 新規相間移動触媒を用いたオレフィン類の不斉フッ素官能基化反応の開発2016

    • Author(s)
      丹羽智紀、浅田純司、佐藤健太郎、橋爪大輔、江上寛通、川戸勇士、濱島義隆
    • Organizer
      フルオラス科学研究会第9回シンポジウム
    • Place of Presentation
      名古屋大学
    • Year and Date
      2016-10-07
    • Related Report
      2016 Annual Research Report
  • [Remarks] 静岡県立大学医薬品創製化学分野

    • URL

      http://w3pharm.u-shizuoka-ken.ac.jp/lsocus/

    • Related Report
      2018 Annual Research Report
  • [Remarks] 静岡県立大学医薬品創製化学分野

    • URL

      http://w3pharm.u-shizuoka-ken.ac.jp/lsocus/publication.html

    • Related Report
      2017 Annual Research Report
  • [Remarks] 静岡県立大学薬学部 医薬品創製化学分野

    • URL

      http://w3pharm.u-shizuoka-ken.ac.jp/lsocus/

    • Related Report
      2016 Annual Research Report

URL: 

Published: 2016-04-21   Modified: 2020-03-30  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi