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Catalytic Asymmetric Synthesis of Chiral Fluorinated Molecules

Research Project

Project/Area Number 23750111
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Synthetic chemistry
Research InstitutionToyohashi University of Technology

Principal Investigator

SHIBATOMI Kazutaka  豊橋技術科学大学, 大学院・工学研究科, 助教 (00378259)

Project Period (FY) 2011 – 2012
Project Status Completed (Fiscal Year 2012)
Budget Amount *help
¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2012: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Fiscal Year 2011: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Keywords有機合成 / フッ素化学 / 不斉合成 / ルイス酸触媒 / Diels-Alder反応 / マイケル付加反応 / フッ素化合物 / トリフルオロメチル基 / シキミ酸 / 光学活性触媒
Research Abstract

Introduction of a trifluoromethyl group into biologically active compounds often modifies their physical and/or biological properties. Here, we have succeeded in the enantioselective Diels-Alder reaction of β-trifluoromethylacrylates to give corresponding cyclohexenes having a trifluoromethyl group at the chiral carbon center. We also demonstrated the organocatalytic asymmetric 1,4-addition of 4,4,4-trifluorocrotonaldehyde.The resulting adducts could be converted into potential synthetic intermediates for new drug candidates.

Report

(3 results)
  • 2012 Annual Research Report   Final Research Report ( PDF )
  • 2011 Research-status Report
  • Research Products

    (25 results)

All 2013 2012 2011 Other

All Journal Article (4 results) (of which Peer Reviewed: 4 results) Presentation (15 results) (of which Invited: 2 results) Book (2 results) Remarks (2 results) Patent(Industrial Property Rights) (2 results)

  • [Journal Article] Copper(II)-Catalyzed Enantioselective Fluorination of ss-Keto Esters Using Chiral Spiro Oxazoline Ligands2013

    • Author(s)
      Akira Narayama, Kazutaka Shibatomi, Yoshinori Soga, Tsubasa Muto, Seiji Iwasa
    • Journal Title

      Synlett

      Volume: Vol.24 Issue: 03 Pages: 375-378

    • DOI

      10.1055/s-0032-1318027

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Practical Synthesis of 4,4,4-Trifluorocrotonaldehyde: A Versatile Precursor for the Enantioselective Formation of Trifluoromethylated Stereogenic Centers via Organocatalytic 1,4-Additions2012

    • Author(s)
      Kazutaka Shibatomi, Akira Narayama, Yoshiyuki Abe, Seiji Iwasa
    • Journal Title

      Chemical Communications

      Volume: Vol.48 Issue: 59 Pages: 7380-7382

    • DOI

      10.1039/c2cc32757k

    • Related Report
      2012 Annual Research Report 2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Highly Enantioselective Chlorination of ss-Ketoesters and Subsequent S_n2 Displacement of Tertiary Chlorides: A Flexible Method for the Construction of Quaternary Stereogenic Centers2012

    • Author(s)
      Kazutaka Shibatomi, Yoshinori Soga, Akira Narayama, Ikuhide Fujisawa, Seiji Iwasa
    • Journal Title

      Journal of the American Chemical Society

      Volume: Vol.134 Issue: 24 Pages: 9836-9839

    • DOI

      10.1021/ja304806j

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] A Diels-Alder Approach to the Enantioselective Construction of Fluoromethylated Stereogenic Carbon Centers2012

    • Author(s)
      Kazutaka Shibatomi, Fumito Kobayashi, Akira Narayama, Ikuhide Fujisawa, Seiji Iwasa
    • Journal Title

      Chemical Communications

      Volume: Vol.48 Issue: 3 Pages: 413-415

    • DOI

      10.1039/c1cc15889a

    • Related Report
      2012 Final Research Report 2011 Research-status Report
    • Peer Reviewed
  • [Presentation] Enantioselective Construction of Halogenated Stereogenic Centers2013

    • Author(s)
      Kazutaka Shibatomi
    • Organizer
      Special Lecture on Organic Chemistry at ETH
    • Place of Presentation
      チューリッヒ工科大学(スイス)
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Copper(II)-Catalyzed Enantioselective Chlorination of Active Methine Compounds Using Chiral Spiro Oxazoline Ligands and Subsequent S_n2 Displacement at the Tertiary Carbon2012

    • Author(s)
      A Diels-Alder Approach to the Enantioselective Construction of Fluoromethylated Stereogenic Carbon Centers
    • Organizer
      2th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-12)
    • Place of Presentation
      京都リーガロイヤルホテル
    • Related Report
      2012 Final Research Report
  • [Presentation] スピロ型キラルオキサゾリン配位子を用いた活性メチン化合物の不斉ハロゲン化反応2012

    • Author(s)
      柴富一孝、楢山輝、曽我宜賀、岩佐精二
    • Organizer
      第42回複素環化学討論会
    • Place of Presentation
      京都テルサ
    • Related Report
      2012 Final Research Report
  • [Presentation] ルイス酸触媒を用いた活性メチン化合物の不斉塩素化反応とそれに続く三級塩素化物の立体特異的求核置換反応2012

    • Author(s)
      柴富一孝、曽我宜賀、楢山輝、岩佐精二
    • Organizer
      第59回有機金属化学討論会
    • Place of Presentation
      大阪大学吹田キャンパス
    • Related Report
      2012 Final Research Report
  • [Presentation] Building Block Approaches for The Enantioselective Construction of Trifluoromethylated Stereogenic Centers2012

    • Author(s)
      Kazutaka Shibatomi, Akira Narayama, Fumito Kobayashi, Seiji Iwasa
    • Organizer
      20 th International Symposium on Fluorine Chemistry
    • Place of Presentation
      京都テルサ
    • Related Report
      2012 Final Research Report
  • [Presentation] フッ素化およびフルオロメチル化された不斉炭素の立体選択的構築法2012

    • Author(s)
      柴富一孝
    • Organizer
      第9回相模フッ素セミナー
    • Place of Presentation
      相模中央研究所
    • Related Report
      2012 Final Research Report
  • [Presentation] Asymmetric Michael Addition of 4,4,4-Trifluorocrotonaldehyde for the Construction of Trifluoromethylated Chiral Stereogenic Centers2012

    • Author(s)
      Kazutaka Shibatomi
    • Organizer
      12th International Kyoto Conference on New Aspects of Organic Chemistry
    • Place of Presentation
      京都リーガロイヤルホテル
    • Related Report
      2012 Annual Research Report
  • [Presentation] Building Block Approaches for The Enantioselective Construction of Trifluoromethylated Stereogenic Centers2012

    • Author(s)
      Kazutaka Shibatomi
    • Organizer
      20th International Symposium on Fluorine Chemistry
    • Place of Presentation
      京都テルサ
    • Related Report
      2012 Annual Research Report
  • [Presentation] フッ素化およびフルオロメチル化された不斉炭素の立体選択的構築法2012

    • Author(s)
      柴富一孝
    • Organizer
      第9回フッ素相模セミナー
    • Place of Presentation
      相模中央研究所
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] β-フルオロメチルアクリル酸エステルの不斉 Diels-Alder 反応2011

    • Author(s)
      柴富一孝、小林史人、楢山輝、岩佐精二
    • Organizer
      第58回有機金属化学討論会
    • Place of Presentation
      名古屋大学東山キャンパス
    • Related Report
      2012 Final Research Report
  • [Presentation] β-フルオロメチルアクリル酸エステルをジエノフィルとした高エナンチオ選択的Diels-Alder 反応2011

    • Author(s)
      柴富一孝、小林史人、楢山輝、岩佐精二
    • Organizer
      第35回フッ素化学討論会
    • Place of Presentation
      岡山大学
    • Related Report
      2012 Final Research Report
  • [Presentation] キラルオキサザボロリジン触媒を用いた不斉 Diels-Alder 反応によるトリフルオロメチル化合物の合成2011

    • Author(s)
      柴富一孝、小林史人、楢山輝、岩佐精二
    • Organizer
      日本化学会第91春期年会
    • Place of Presentation
      神奈川大学横浜キャンパス
    • Related Report
      2012 Final Research Report
  • [Presentation] Enantioselective Synthesis of Organo-fluorine Compounds2011

    • Author(s)
      柴富一孝
    • Organizer
      分子科学研究所オープンセミナー(招待講演)
    • Place of Presentation
      分子科学研究所(愛知)
    • Related Report
      2011 Research-status Report
  • [Presentation] Enantioselective Diels-Alder Reaction of β-Fluoromethylacrylates2011

    • Author(s)
      柴富一孝、小林史人、楢山輝、岩佐精二
    • Organizer
      第58回有機金属化学討論会
    • Place of Presentation
      名古屋大学(愛知)
    • Related Report
      2011 Research-status Report
  • [Presentation] β-フルオロメチルアクリル酸エステルをジエノフィルとした高エナンチオ選択的Diels-Alder反応2011

    • Author(s)
      柴富一孝、小林史人、楢山輝、岩佐精二
    • Organizer
      第35回フッ素化学討論会
    • Place of Presentation
      岡山大学(岡山)
    • Related Report
      2011 Research-status Report
  • [Book] 光学活性医薬品開発とキラルプロセス化学技術-法規制・特許・品質管理・工業化の留意点-第4部第3章「進化する触媒的不斉合成」2011

    • Author(s)
      柴富一孝
    • Publisher
      サイエンス&テクノロジー株式会社
    • Related Report
      2012 Final Research Report
  • [Book] 光学活性医薬品開発とキラルプロセス化学技術―法規制・特許・品質管理・工業化の留意点- 第4部第3章 進化する触媒的不斉合成2011

    • Author(s)
      柴富一孝
    • Total Pages
      19
    • Publisher
      サイエンス&テクノロジー株式会社
    • Related Report
      2011 Research-status Report
  • [Remarks]

    • URL

      http://ens.tut.ac.jp/orgchem/index.html

    • Related Report
      2012 Final Research Report
  • [Remarks]

    • URL

      http://www.tutms.tut.ac.jp/STAFF/SHIBATOMI/pub.html.ja

    • Related Report
      2011 Research-status Report
  • [Patent(Industrial Property Rights)] 含フッ素α,β-不飽和アルデヒドの製造方法および含フッ素α,β-不飽和アルデヒドを用いた光学活性含フッ素化合物の製造方法2013

    • Inventor(s)
      柴富一孝
    • Industrial Property Rights Holder
      柴富一孝
    • Industrial Property Number
      2012-052188
    • Filing Date
      2013-03-08
    • Related Report
      2012 Final Research Report
  • [Patent(Industrial Property Rights)] 含フッ素α,β-不飽和アルデヒドの製造方法および含フッ素α,β-不飽和アルデヒドを用いた光学活性含フッ素化合物の製造方法2012

    • Inventor(s)
      柴富一孝
    • Industrial Property Rights Holder
      国立大学法人豊橋技術科学大学
    • Industrial Property Number
      2012-052188
    • Filing Date
      2012
    • Related Report
      2011 Research-status Report

URL: 

Published: 2011-08-05   Modified: 2019-07-29  

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