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Development of aerobic alcohol oxidation systems based on nitroxyl radical-Cu catalysis

Research Project

Project/Area Number 24390001
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypePartial Multi-year Fund
Section一般
Research Field Chemical pharmacy
Research InstitutionTohoku University

Principal Investigator

IWABUCHI Yoshiharu  東北大学, 薬学研究科(研究院), 教授 (20211766)

Project Period (FY) 2012-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥18,720,000 (Direct Cost: ¥14,400,000、Indirect Cost: ¥4,320,000)
Fiscal Year 2014: ¥5,200,000 (Direct Cost: ¥4,000,000、Indirect Cost: ¥1,200,000)
Fiscal Year 2013: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2012: ¥8,450,000 (Direct Cost: ¥6,500,000、Indirect Cost: ¥1,950,000)
Keywords空気酸化 / アルコール酸化 / 酸化触媒 / 銅ニトロキシド / 不斉酸化 / 化学選択性
Outline of Final Research Achievements

We have successfully developed the highly chemoslective aerobic alcohol oxidation using nitroxyl radical-copper catalysis that realize an efficient transformation of an unprotected amino-alcohol into the corresponding amino-carabonyl compound. We have identified the optimum combination of nitroxyl radical, copper salt, and solution concentration dependent on the type of substrate. Useful information of the catalyst structure-enantioselectivity relationship has been obtained, which will lead the development of an enantioselective aerobic oxidation system.

Report

(4 results)
  • 2014 Annual Research Report   Final Research Report ( PDF )
  • 2013 Annual Research Report
  • 2012 Annual Research Report

Research Products

(21 results)

All 2015 2014 2013 Other

All Journal Article (8 results) (of which Peer Reviewed: 8 results,  Acknowledgement Compliant: 4 results) Presentation (12 results) (of which Invited: 3 results) Remarks (1 results)

  • [Journal Article] Highly Efficient Aerobic Oxidation of Alcohols by Using Less-Hindered Nitroxyl-Radical/Copper Catalysis: Optimum Catalyst Combinations and Their Substrate Scope2015

    • Author(s)
      Sasano, Y.; Kogure, N.; Nishiyama, T.; Nagasawa, S.; Iwabuchi, Y.
    • Journal Title

      Chemistry-An Asian Journal

      Volume: 10 Pages: 1004-1009

    • DOI

      10.1002/asia.201403245

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Development of an Azanoradamantane-Type Nitroxyl Radical Catalyst for Class-Selective Oxidation of Alcohols2015

    • Author(s)
      Ryusuke Doi, Masatoshi Shibuya, Tsukasa Murayama, Yoshihiko Yamamoto, Yoshiharu Iwabuchi
    • Journal Title

      The Journal of Organic Chemsitry

      Volume: 80 Pages: 401-413

    • DOI

      10.1021/jo502426p

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Mechanistic Insight into Aerobic Alcohol Oxidation Using NOx-Nitroxide Catalysis Based on Catalyst Structure-Activity Relationships2014

    • Author(s)
      Shibuya, M.; Nagasawa, S.; Osada, Y.; Iwabuchi, Y.
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 79 Pages: 10256-10268

    • DOI

      10.1021/jo501862k

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Highly Enantioselective Organocatalytic Oxidative Kinetic Resolution of Secondary Alcohols Using Chiral Alkoxyamines as Precatalysts: Catalyst Structure, Active Species, and Substrate Scope2014

    • Author(s)
      Keiichi Murakami, Yusuke Sasano, Masaki Tomizawa, Masatoshi Shibuya, Eunsang Kwon, Yoshiharu Iwabuchi
    • Journal Title

      Journal of the American Chemical Society

      Volume: 136 Pages: 17591-17600

    • DOI

      10.1021/ja509766f

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Highly Chemoselective Aerobic Oxidation of Amino Alcohols into Amino Carbonyl Compounds2014

    • Author(s)
      Yusuke Sasano, Shota Nagasawa, Mai Yamazaki, Masatoshi Shibuya, Yoshiharu Iwabuchi
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 53 Pages: 3236-3240

    • DOI

      10.1002/anie.201309634

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 3-Methyl-4-Oxa-5-Azahomoadamantane: Alkoxyamine-Type Organocatalyst for Alcohol Oxidation2013

    • Author(s)
      Yusuke Sasano, Keiichi Murakami, Tomohiro Nishiyama, Eunsang Kwon, Yoshiharu Iwabuchi
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 52 Pages: 12624-12627

    • DOI

      10.1002/anie.201307144

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] C-H Modification of 2-Azaadamantane: Synthesis of C5-Functionalized AZADOs for Advanced Use2013

    • Author(s)
      Yusuke Sasano, Tomohiro Nishiyama, Masaki Tomizawa, Masatoshi Shibuya, Yoshiharu Iwabuchi
    • Journal Title

      Heterocycles

      Volume: 87 Pages: 2109-2118

    • DOI

      10.3987/com-13-12804

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Discovery and Exploitation of AZADO: The Highly Active Catalyst for Alcohol Oxidation2013

    • Author(s)
      Yoshiharu Iwabuchi
    • Journal Title

      CHEMICAL & PHARMACEUTICAL BULLETIN

      Volume: 61 Issue: 12 Pages: 1197-1213

    • DOI

      10.1248/cpb.c13-00456

    • NAID

      130003381786

    • ISSN
      0009-2363, 1347-5223
    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Presentation] 有機ニトロキシルラジカル-銅触媒系を用いたアルコール空気酸化反応条件の最適化2015

    • Author(s)
      小暮直貴,笹野裕介,西山智弘,長澤翔太,岩渕好治
    • Organizer
      日本薬学会第135年会
    • Place of Presentation
      神戸学院大学
    • Year and Date
      2015-03-25 – 2015-03-28
    • Related Report
      2014 Annual Research Report
  • [Presentation] AZADO-銅触媒系によるアミノアルコール類の高化学選択的空気酸化反応の開発と応用2014

    • Author(s)
      長澤翔太,笹野裕介,澁谷正俊,Jaiwook Park, 岩渕好治
    • Organizer
      第40回反応と合成の進歩シンポジウム
    • Place of Presentation
      仙台国際センター
    • Year and Date
      2014-11-10 – 2014-11-11
    • Related Report
      2014 Annual Research Report
  • [Presentation] Development of AZADO: The highly active organocatalyst for alcohol oxidation2014

    • Author(s)
      Yoshiharu Iwabchi
    • Organizer
      The 24th French-Japanese Symposium on Medicinal and Fine Chemsitry
    • Place of Presentation
      University Claude Bernard Lyon 1, France
    • Year and Date
      2014-09-14 – 2014-09-17
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] AZADO-銅触媒系を用いたアミノアルコール類の高化学選択的空気酸化反応2014

    • Author(s)
      長澤翔太、笹野裕介、澁谷正俊、岩渕好治
    • Organizer
      第25回記念万有仙台シンポジウム
    • Place of Presentation
      仙台国際センター
    • Year and Date
      2014-06-14
    • Related Report
      2014 Annual Research Report
  • [Presentation] Highly Chemoselective Aerobic Oxidation of Amino Alcohols to Amino Carbonyl Compounds2014

    • Author(s)
      Yoshiharu Iwbuchi
    • Organizer
      The International Startup Symposium of Cutting-Edge Organic Chemistry in Asia (III)
    • Place of Presentation
      National Tsing Hua University, Hsinchu, Taiwan
    • Year and Date
      2014-04-19 – 2014-04-21
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Discovery and Exploitation of AZADO: The Highly Active Organocatalyst of Alcohol Oxidation2014

    • Author(s)
      Yoshiharu Iwabuchi
    • Organizer
      FloHet-2014 Florida Heterocyclic and Synthetic Conference
    • Place of Presentation
      University of Florida, USA
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] AZADO一銅触媒系を用いたアミノアルコール類の高化学選択的空気反応の開発と応用2013

    • Author(s)
      長澤翔太、笹野裕介、澁谷正俊、岩渕好抬
    • Organizer
      日本薬学会第133年会
    • Place of Presentation
      パシフィコ横浜
    • Year and Date
      2013-03-30
    • Related Report
      2012 Annual Research Report
  • [Presentation] Highly Chemoselective Aerobic Oxidation of Alcohols by AZADO-Copper Catalytic Systems2013

    • Author(s)
      Yusuke Sasano, Shota Nagasawa, Tomohiro Nishiyama, Masatoshi Shibuya, Yoshiharu Iwabuchi
    • Organizer
      4th UK/Japan Conference in Catalytic Asymmetric Synthesis
    • Place of Presentation
      仙台国際センター
    • Related Report
      2013 Annual Research Report
  • [Presentation] AZADO-銅協奏型触媒を用いたアミノアルコール類の高化学選択的空気酸化反応2013

    • Author(s)
      笹野 裕介・長澤 翔太・西山 智弘・澁谷 正俊・岩渕 好治
    • Organizer
      日本プロセス化学会2013サマーシンポジウム
    • Place of Presentation
      つくば国際会議場
    • Related Report
      2013 Annual Research Report
  • [Presentation] AZADO-銅協奏型触媒を用いたアルコール類の空気酸化反応2013

    • Author(s)
      西山智弘,笹野裕介,長澤翔太,岩渕好治
    • Organizer
      第52回日本薬学会東北支部大会
    • Place of Presentation
      東北大学
    • Related Report
      2013 Annual Research Report
  • [Presentation] AZADO を触媒とするアルコール類の高効率的空気酸化反応の開発と応用2013

    • Author(s)
      長澤翔太,長田祐二,西山智弘,笹野裕介,澁谷正俊,岩渕好治
    • Organizer
      第3回CSJ化学フェスタ2013
    • Place of Presentation
      タワーホール船堀
    • Related Report
      2013 Annual Research Report
  • [Presentation] AZADO-銅触媒系を用いるアミノアルコール類の高化学選択的空気酸化反応2013

    • Author(s)
      長澤翔太,笹野裕介,西山智弘,澁谷正俊,岩渕好治
    • Organizer
      第46回酸化反応討論会
    • Place of Presentation
      筑波大学
    • Related Report
      2013 Annual Research Report
  • [Remarks] 東北大学大学院薬学研究科合成制御化学分野ホームページ

    • URL

      http://www.pharm.tohoku.ac.jp/~gousei/synthetic/index.html

    • Related Report
      2014 Annual Research Report

URL: 

Published: 2012-04-23   Modified: 2019-07-29  

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