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Development of novel synthetic methods controlled by the reduction potential of substrates and the reactivity of leaving groups in the reaction media

Research Project

Project/Area Number 16K05768
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionNagaoka University of Technology

Principal Investigator

MAEKAWA Hirofumi  長岡技術科学大学, 工学研究科, 教授 (70283041)

Co-Investigator(Kenkyū-buntansha) 山本 祥正  東京工業高等専門学校, 機械工学科, 准教授 (90444190)
Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2018: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Keywordsマグネシウム / 電子移動 / 還元 / 環境調和 / 有機合成 / カップリング / 脱離基 / 合成化学 / 元素戦略 / 環境調和型反応
Outline of Final Research Achievements

In this research, magnesium was used as a reducing agent in synthetic organic reactions, which was commercially available and cheap. Aromatic compounds with a leaving group on a vinyl carbon atom were prepared and substitution reactions of the leaving group were investigated under the conditions of Mg-promoted reduction. As a result, the leaving group was replaced with a silyl group when a cinnamic acid ester with a leaving group at beta-position of the carbonyl group was reduced in THF. The silylated compound was further reduced in NMP in the presence of another nucleophile to give a variety of compounds with two functional groups at the benzylic position. Reduction of aliphatic conjugated esters and styrenes with a leaving group also gave substitution compounds under the similar reaction conditions.

Academic Significance and Societal Importance of the Research Achievements

有機合成反応は,日常生活に使われる様々な有機物質や有機材料,さらにはそれらの中間体を合成する重要な手法である。歴史は古く,これまでに無数の反応が開発されているが,バイオマスなどの石油代替資源を有効に活用して今後も安価に自由自在に有機物質を合成するには,さらなる有機物質構造変換法の開発が必要である。遷移金属錯体を用いる有機合成と比べて電子移動を用いた有機合成反応分野は研究者数が少ないが,相補的に幅広く有機合成分野を網羅する上で不可欠な技術分野である。また本研究で還元剤として用いたマグネシウムは地球上に広く分布し,入手容易であるため,その有機合成への活用は我が国の元素戦略上も有益である。

Report

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

    (24 results)

All 2019 2018 2017 2016 Other

All Journal Article (5 results) (of which Peer Reviewed: 5 results,  Acknowledgement Compliant: 2 results) Presentation (17 results) (of which Int'l Joint Research: 3 results,  Invited: 2 results) Remarks (2 results)

  • [Journal Article] Selective Introduction of Trifluoroacetyl Group to beta- and gamma-Position of Aromatic Conjugated Esters: Facile Synthesis of Fluorine-containing Keto Esters2019

    • Author(s)
      Tianyuan Zhang, Yuhei Shimizu, Kazuyuki Shimizu, Mitsuhiro Abe, Suhua Zheng, Hirofumi Maekawa
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 8 Issue: 3 Pages: 344-347

    • DOI

      10.1002/ajoc.201800741

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalyst-Free and Solvent-Controlled Reductive Coupling of Activated Vinyl Triflates with Chlorotrimethylsilane by Magnesium Metal and Its Synthetic Application2018

    • Author(s)
      Hirofumi Maekawa, Katsuaki Noda, Keisuke Kuramochi, Tianyuan Zhang
    • Journal Title

      Organic Letters

      Volume: 20 Issue: 7 Pages: 1953-1956

    • DOI

      10.1021/acs.orglett.8b00496

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of 4-Trifluoromethylcyclopentenones and 2-Trifluoromethylfurans by Reductive Trifluoroacetylation of Ynones2017

    • Author(s)
      Tianyuan Zhang, Hirofumi Maekawa
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 24 Pages: 6602-6605

    • DOI

      10.1021/acs.orglett.7b03302

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Reductive carboxylation of aromatic esters by electron transfer from magnesium metal2017

    • Author(s)
      Hirofumi Maekawa, Hikaru Okawara, Taro Murakami
    • Journal Title

      Tetrahedron Letters

      Volume: 58 Issue: 3 Pages: 206-209

    • DOI

      10.1016/j.tetlet.2016.12.001

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] マグネシウム金属還元法の新たな炭素ー炭素結合および炭素ーケイ素結合形成への応用2017

    • Author(s)
      前川博史
    • Journal Title

      有機合成化学協会誌

      Volume: 75 Pages: 240-252

    • NAID

      130005549312

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] 1-ベンゾフラン-2-カルボン酸メチル類のマグネシウム還元シリル化反応2019

    • Author(s)
      鄭素華,張田原,前川博史
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] アルケン部位に脱離基を有する芳香族炭化水素とアクリル酸エステルのマグネシウム還元カップリング反応2019

    • Author(s)
      松尾洸弥,張田原,前川博史
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] エステルのβ位に脱離基を有する桂皮酸エチル類とアクリル酸メチルのマグネシウム還元カップリング反応2019

    • Author(s)
      田中寿史,張田原,前川博史
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] マグネシウム還元法によるエステルのβ位に脱離基を有する脂 肪族共役エステルとアクリル酸エステルのカップリング反応2018

    • Author(s)
      長谷川智也,張田原,前川博史
    • Organizer
      第75回有機合成化学協会関東支部シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] 金属マグネシウム還元による2-アセチルベンゾフラン類の選択的シリル化反応2018

    • Author(s)
      鄭素華,張田原,前川博史
    • Organizer
      第76回有機合成化学協会関東支部シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] Facile synthesis of 2-trifluoromethylfurans by reductive trifluoroacetylation of ynones2018

    • Author(s)
      張田原,前川博史
    • Organizer
      第42回有機電子移動化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Reductive Silylation of Conjugated Esters with a Leaving Group at β-Position by Magnesium Metal2018

    • Author(s)
      Hirofumi Maekawa
    • Organizer
      The 13th International Symposium on Organic Reactions
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] エステルのβ位に脱離基を有する脂肪族共役エステルとアクリル酸 エステルのマグネシウム還元カップリング反応2018

    • Author(s)
      長谷川智也、張 田原、前川博史
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] β位に脱離基を有する脂肪族共役エステルのマグネシウム還元シリル化反応2017

    • Author(s)
      吉澤美沙紀,五十嵐友紀,野田克哲,前川博史
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学
    • Year and Date
      2017-03-18
    • Related Report
      2016 Research-status Report
  • [Presentation] マグネシウム還元法による脱離基を有するスチレンのシリル化反応2017

    • Author(s)
      田原正太,前川博史
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学
    • Year and Date
      2017-03-17
    • Related Report
      2016 Research-status Report
  • [Presentation] 脂肪族α, β-不飽和エステルと桂皮酸エチル類のマグネシウム還元カップリング反応2017

    • Author(s)
      土門千紗,倉持圭佑,前川博史
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学
    • Year and Date
      2017-03-17
    • Related Report
      2016 Research-status Report
  • [Presentation] Development of a precise and reliable synthetic process of organic fine-chemicals through reductive coupling reaction of vinyl triflates2017

    • Author(s)
      Hirofumi Maekawa
    • Organizer
      1st International Symposium on Future Innovative Reliable Materials
    • Place of Presentation
      Nagaoka University of Technology
    • Year and Date
      2017-03-10
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] β位に脱離基を有するα、βー不飽和エステルのマグネシウム還元炭素ーケイ素、炭素ー炭素結合形成反応2017

    • Author(s)
      前川博史、野田克哲、土門千紗、吉澤美沙紀、倉持圭佑
    • Organizer
      第73回有機合成化学協会関東支部シンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] マグネシウム還元法によるβ位に脱離基を有する桂皮酸エステル類への選択的官能基導入反応2017

    • Author(s)
      前川博史、野田克哲、土門千紗、吉澤美沙紀、倉持圭佑
    • Organizer
      第41回有機電子移動化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 脱離基を有するスチレンのマグネシウム還元シリル化反応2017

    • Author(s)
      田原正太、前川博史
    • Organizer
      第74回有機合成化学協会関東支部シンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] 脱離基を有するスチルベンのマグネシウム還元シリル化反応2016

    • Author(s)
      中嶋木乃美,前川博史
    • Organizer
      第72回有機合成化学協会関東支部シンポジウム
    • Place of Presentation
      新潟薬科大学
    • Year and Date
      2016-11-27
    • Related Report
      2016 Research-status Report
  • [Presentation] Regioselective Introduction of Electrophiles to the Olefinic β-Position of 4-Vinylpyridines by Mg-Promoted Reduction2016

    • Author(s)
      Hirofumi Maekawa
    • Organizer
      The 12th International Symposium on Organic Reactions
    • Place of Presentation
      Kyoto Terrsa
    • Year and Date
      2016-04-23
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Remarks] 研究者総覧

    • URL

      http://souran.nagaokaut.ac.jp/view?l=ja&u=164&i=j30&sm=name&sl=ja&sp=1

    • Related Report
      2017 Research-status Report
  • [Remarks] 研究者総覧

    • URL

      http://souran.nagaokaut.ac.jp/view?l=ja&u=164&f1=09&f2=46&sm=field&sl=ja&sp=1

    • Related Report
      2016 Research-status Report

URL: 

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

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