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Asymmetric induction by using carbocations as a reactive species

Research Project

Project/Area Number 26670001
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Chemical pharmacy
Research InstitutionKanazawa University

Principal Investigator

KUNISHIMA MUNETAKA  金沢大学, 薬学系, 教授 (10214975)

Co-Investigator(Kenkyū-buntansha) KITAMURA Masanori  金沢大学, 医薬保健研究域薬学系, 准教授 (80453835)
Project Period (FY) 2014-04-01 – 2016-03-31
Project Status Completed (Fiscal Year 2015)
Budget Amount *help
¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Fiscal Year 2015: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2014: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
KeywordsAsymmetric induction / Carbocations / カルボカチオン / 不斉アルキル化 / 脱離基 / 脱水縮合剤
Outline of Final Research Achievements

Asymmetric induction utilizing highly reactive carbocations is an attractive and challenging theme. We hypothesized that if an optically active asymmetric ether coordinates to a prochiral carbocation in a face-selective manner, stereoselectivity can be achieved in alkylation of nucleophiles. As a result, we succeeded in development of various reagents that enable to generate carbocationic species available for the study of asymmetric induction. In addition, in a Friedel-Crafts reaction using phenethylcationic species in the presence of an asymmetric ether, we observed asymmetric induction even though the selectivity was insufficient.

Report

(3 results)
  • 2015 Annual Research Report   Final Research Report ( PDF )
  • 2014 Research-status Report
  • Research Products

    (16 results)

All 2015 2014

All Journal Article (3 results) (of which Peer Reviewed: 3 results,  Acknowledgement Compliant: 1 results) Presentation (11 results) (of which Int'l Joint Research: 3 results) Patent(Industrial Property Rights) (2 results)

  • [Journal Article] Study of the Reactivities of Acid-Catalyzed O-Benzylating Reagents Based on Structural Isomers of 1,3,5-Triazine2015

    • Author(s)
      Hikaru Fujita, Naoko Hayakawa, and Munetaka Kunishima
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 80 Issue: 21 Pages: 11200-11205

    • DOI

      10.1021/acs.joc.5b02059

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] O-Benzylation of Carboxylic Acids Using 2,4,6-Tris(benzyloxy)-1,3,5-triazine (TriBOT) under Acidic or Thermal Conditions2015

    • Author(s)
      Kohei Yamada, Saki Yoshida, Hikaru Fujita, Masanori Kitamura, and Munetaka Kunishima
    • Journal Title

      European Journal of Organic Chemistry

      Volume: 36 Issue: 36 Pages: 7997-8002

    • DOI

      10.1002/ejoc.201501172

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Development of a New Benzylating Reagent Spontaneously Releasing Benzyl Cation Equivalents at Room Temperature2014

    • Author(s)
      Kohei Yamada, Yuichi Tsukada, Yukiko Karuo, Masanori Kitamura, Munetaka Kunishima
    • Journal Title

      Chem. Eur. J.

      Volume: 20 Issue: 38 Pages: 12274-12278

    • DOI

      10.1002/chem.201403158

    • Related Report
      2014 Research-status Report
    • Peer Reviewed
  • [Presentation] Study of the reactivity of benzyloxytriazine derivatives (BOTs) for acid catalyzed O-benzylation2015

    • Author(s)
      Fujita H, Kunishima M.
    • Organizer
      2015 International Chemical Congress of Pacific Basin Societies
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      2015-12-16
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Quick and mild methods for cleavage of amide-bonds by using a triazine-based benzylating reagent2015

    • Author(s)
      Karuo Y, Yamada K, Kunishima M.
    • Organizer
      2015 International Chemical Congress of Pacific Basin Societies
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      2015-12-16
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 新規酸触媒トリアジノン型ベンジル化剤の開発2015

    • Author(s)
      角山哲史, 藤田光, 北村正典, 山田耕平, 国嶋崇隆
    • Organizer
      第45回複素環化学討論会
    • Place of Presentation
      早稲田大学、東京
    • Year and Date
      2015-11-20
    • Related Report
      2015 Annual Research Report
  • [Presentation] トリアジン型酸触媒ベンジル化剤のジプロトン化機構によるO-ベンジル化反応2015

    • Author(s)
      藤田光, 国嶋崇隆
    • Organizer
      第41回反応と合成の進歩シンポジウム
    • Place of Presentation
      近畿大学、大阪
    • Year and Date
      2015-10-27
    • Related Report
      2015 Annual Research Report
  • [Presentation] Development of acid-catalyzed alkylating reagents based on triazine chemistry2015

    • Author(s)
      Hayakawa N, Yamada K, Fujita H, Kitamura M, Yoshimura K, Kunishima M.
    • Organizer
      The 3rd International Symposium on Process Chemistry
    • Place of Presentation
      Kyoto International Conference Center, Kyoto, Japan
    • Year and Date
      2015-07-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] トリアジン骨格を基盤とする酸触媒tert-ブチル化剤の開発2015

    • Author(s)
      早川奈緒子、山田耕平、藤田光、国嶋崇隆
    • Organizer
      日本薬学会第135年会
    • Place of Presentation
      神戸、神戸学院大学
    • Year and Date
      2015-03-26
    • Related Report
      2014 Research-status Report
  • [Presentation] アミノトリアジンを脱離基とするベンジル化剤の開発:置換基効果に基づく分解反応の制御2015

    • Author(s)
      軽尾友紀子、小峰彩、北村正典、国嶋崇隆
    • Organizer
      日本薬学会第135年会
    • Place of Presentation
      神戸、神戸学院大学
    • Year and Date
      2015-03-26
    • Related Report
      2014 Research-status Report
  • [Presentation] Development of a new benzylating reagent which releases benzyl cation-like species at room temperature2014

    • Author(s)
      Kohei Yamada, Yukiko Karuo, Yuichi Tsukada, Masanori Kitamura, Munetaka Kunishima
    • Organizer
      14th Tetrahedron Symposium Asia Edition
    • Place of Presentation
      Singapore、Singapore EXPO Convention and Exhibition Centre
    • Year and Date
      2014-10-30
    • Related Report
      2014 Research-status Report
  • [Presentation] 電子欠乏性アミノトリアジンを脱離基としたベンジル化剤の開発2014

    • Author(s)
      軽尾友紀子, 塚田裕以智, 山田耕平, 北村正典, 国嶋崇隆
    • Organizer
      第44回複素環化学討論会
    • Place of Presentation
      北海道、札幌市民ホール
    • Year and Date
      2014-09-11
    • Related Report
      2014 Research-status Report
  • [Presentation] 酸触媒ベンジル化剤TriBOTを用いた低環境負荷型エステル化反応の開発2014

    • Author(s)
      山田耕平、吉田紗季、吉村和真、藤田光、北村正典、河合伸高、国嶋崇隆
    • Organizer
      日本プロセス化学会 2014 サマーシンポジウム
    • Place of Presentation
      東京、タワーホール船堀
    • Year and Date
      2014-08-01
    • Related Report
      2014 Research-status Report
  • [Presentation] ベンジルカチオン種の求電子付加に基づくアミド結合開裂反応の開発2014

    • Author(s)
      軽尾友紀子,山田耕平,北村正典,国嶋崇隆
    • Organizer
      創薬懇話会 2014 in 岐阜
    • Place of Presentation
      岐阜、岐阜長良川温泉 ホテルパーク
    • Year and Date
      2014-07-09
    • Related Report
      2014 Research-status Report
  • [Patent(Industrial Property Rights)] トリアジンジオン化合物2015

    • Inventor(s)
      国嶋崇隆
    • Industrial Property Rights Holder
      国立大学法人金沢大学
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2015-208908
    • Filing Date
      2015-10-23
    • Related Report
      2015 Annual Research Report
  • [Patent(Industrial Property Rights)] トリアジン化合物2015

    • Inventor(s)
      国嶋 崇隆
    • Industrial Property Rights Holder
      金沢大学
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2015-037118
    • Filing Date
      2015-02-26
    • Related Report
      2014 Research-status Report

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Published: 2014-04-04   Modified: 2017-05-10  

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