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Development and Application of Dynamic Kinetic Resolution Reaction via chiral pi-allylpalladium complex

Research Project

Project/Area Number 24590029
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Chemical pharmacy
Research InstitutionMusashino University

Principal Investigator

HIROYA Kou  武蔵野大学, 薬学研究所, 教授 (70192721)

Co-Investigator(Kenkyū-buntansha) SHIGEHISA Hiroki  武蔵野大学, 薬学研究所, 助教 (60612471)
Project Period (FY) 2012-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥5,330,000 (Direct Cost: ¥4,100,000、Indirect Cost: ¥1,230,000)
Fiscal Year 2014: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2013: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2012: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Keywords動的光学分割 / 不斉配位子 / パラジウム錯体 / 不斉全合成 / アルカロイド / 動的光学分割反応 / 動的化学分割反応
Outline of Final Research Achievements

We had found dynamic kinetic resolution reaction, which proceeded via pi-allylpalladium complex including unusual carbon-carbon bond formation reaction. Thus, we have started our research to establish the optimized reaction condition and utilize its product for the enantioselective synthesis of biologically active compounds as our object.
As results, we established the synthetic route of the starting material and clarified a requirement of the substrate to obtain high enantioselectivity. Moreover, we successfully optimized the solvent and reaction temperature, and established to generate chiral Pd(0) complex in situ. Although we also clarified both of chemical yields and enantioselectivity are influenced by the electronic effect of the substituent on the aromatic ring, elusidation of the mechanism for DKR is underway. By the way, we successfully achieved the stereoselective construction of the chiral quaternary carbon center on benzylic position.

Report

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

    (20 results)

All 2014 2013 2012 Other

All Journal Article (5 results) (of which Peer Reviewed: 4 results) Presentation (11 results) (of which Invited: 1 results) Remarks (4 results)

  • [Journal Article] Catalytic Hydroamination of Unactivated Olefins Using a Co Catalyst for Complex Molecule Synthesis2014

    • Author(s)
      Hiroki Shigehisa, Natsumi Koseki, Nao Shimizu, Mayu Fujisawa, Makoto Niitsu, Kou Hiroya
    • Journal Title

      Journal of the American Chemical Society

      Volume: 136 Issue: 39 Pages: 13534-13537

    • DOI

      10.1021/ja507295u

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cobalt-Catalyzed Hydrofluorination of Unactivated Olefins: A Radical Approach of Fluorine Transfer.2013

    • Author(s)
      Hiroki Shigehisa, Eriko Nishi, Mayu Fujisawa, Kou Hiroya
    • Journal Title

      Organic Letters

      Volume: 15 Issue: 20 Pages: 5158-5161

    • DOI

      10.1021/ol402696h

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Hydroalkoxylation of Unactivated Olefins with Carbon Radicals and Carbocation Species as Key Intermediates.2013

    • Author(s)
      Hiroki Shigehisa, Tatsuya Aoki, Sumiko Yamaguchi, Nao Shimizu, Kou Hiroya
    • Journal Title

      Journal of the American Chemical Society

      Volume: 135 Issue: 28 Pages: 10306-10309

    • DOI

      10.1021/ja405219f

    • Related Report
      2013 Research-status Report
  • [Journal Article] Stereocontrolled Synthesis of Trichodermatide A2013

    • Author(s)
      Hiroki Shigehisa, Yoshihiro Suwa, Naho Furiya, Yuki Nakaya, Minoru Fukushima, Yusuke Ichihashi, Kou Hiroya
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 52 Issue: 13 Pages: 3646-3649

    • DOI

      10.1002/anie.201210099

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Tandem-type Pd(II)-catalyzed oxidative Heck reaction/intramolecular C-H amidation sequence : a novel route to 4-aryl-2-quinolinones2012

    • Author(s)
      Kiyofumi Inamoto, Junpei Kawasaki, Kou Hiroya, Yoshinori Kondo, Takayuki Doi
    • Journal Title

      Chemical Communications

      Volume: 48 Issue: 36 Pages: 4332-4334

    • DOI

      10.1039/c2cc30600j

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Presentation] コバルト触媒を利用したオレフィンの分子内ヒドロアミノ化反応2014

    • Author(s)
      清水 奈緒,小関 菜摘,藤澤 真優,新津 真琴,重久 浩樹,廣谷 功
    • Organizer
      第58回 日本薬学会関東支部大会
    • Place of Presentation
      昭和薬科大学(東京都町田市)
    • Year and Date
      2014-10-04
    • Related Report
      2014 Annual Research Report
  • [Presentation] コバルト触媒を用いたオレフィンのヒドロフッ素化反応2014

    • Author(s)
      西 恵理子,藤澤 真優,重久 浩樹,廣谷 功
    • Organizer
      第58回 日本薬学会関東支部大会
    • Place of Presentation
      昭和薬科大学(東京都町田市)
    • Year and Date
      2014-10-04
    • Related Report
      2014 Annual Research Report
  • [Presentation] Co錯体/F+試薬/SiH試薬を用いたオレフィンの触媒的分子内ヒドロアミノ化反応2014

    • Author(s)
      重久 浩樹,小関 菜摘,清水 奈緒,藤澤 真優,新津 真琴,廣谷 功
    • Organizer
      第44回 複素環化学討論会
    • Place of Presentation
      札幌市民ホール(札幌市)
    • Year and Date
      2014-09-10 – 2014-09-12
    • Related Report
      2014 Annual Research Report
  • [Presentation] 含窒素ヘテロ環化合物の合成法 ~電子過剰系ヘテロ環化合物を中心に~2014

    • Author(s)
      廣谷 功
    • Organizer
      平成26年度前期(春期)有機合成化学講習会
    • Place of Presentation
      日本薬学会長井記念ホール(東京都渋谷区)
    • Year and Date
      2014-06-18 – 2014-06-19
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] ラジカルとカチオンを経由する不活性オレフィンの触媒的ヒドロアルコキシル化反応2013

    • Author(s)
      青木 竜也,山口 寿美子,清水 奈緒,重久 浩樹,廣谷 功
    • Organizer
      第57回 日本薬学会関東支部大会
    • Place of Presentation
      帝京大学板橋キャンパス(東京都)
    • Related Report
      2013 Research-status Report
  • [Presentation] コバルト錯体と求電子的フッ素化剤を用いた官能基許容性の高いオレフィンへの付加反応2013

    • Author(s)
      重久 浩樹,青木 竜也,山口 寿美子,清水 奈緒,西 恵理子,藤澤 真優,廣谷 功
    • Organizer
      第60回 有機金属化学討論会
    • Place of Presentation
      学習院創立百周年記念会館正堂(東京都)
    • Related Report
      2013 Research-status Report
  • [Presentation] 不斉ジヒドロキシル化―非対称化連続反応を利用するベンジル位不斉第四級炭素構築法の開発2012

    • Author(s)
      廣谷 功,高橋 絵里菜,市橋 佑介,重久 浩樹,土井 隆行
    • Organizer
      第51回 日本薬学会東北支部大会
    • Place of Presentation
      青森大学薬学部(青森市)
    • Related Report
      2012 Research-status Report
  • [Presentation] (–)-Trichodermatide A の全合成2012

    • Author(s)
      重久 浩樹,諏訪 好泰,降矢 奈穂,中谷 有岐,福島 稔,市橋 佑介,廣谷 功
    • Organizer
      第42回 複素環化学討論会
    • Place of Presentation
      京都テルサ(京都市)
    • Related Report
      2012 Research-status Report
  • [Presentation] パラジウム触媒 C-H アミノ化を基盤とする新規 2-キノリノン類合成法の開発2012

    • Author(s)
      稲本 浄文,川崎 順平,齋藤 孔隆,廣谷 功,土井 隆行,根東 義則
    • Organizer
      第42回 複素環化学討論会
    • Place of Presentation
      京都テルサ(京都市)
    • Related Report
      2012 Research-status Report
  • [Presentation] 触媒的不斉導入によるベンジル位不斉第四級炭素構築法の開発研究2012

    • Author(s)
      廣谷 功,高橋 絵里菜,市橋 佑介,重久 浩樹,土井 隆行
    • Organizer
      第42回 複素環化学討論会
    • Place of Presentation
      京都テルサ(京都市)
    • Related Report
      2012 Research-status Report
  • [Presentation] 閉環-官能基化反応による3位ヘテロ原子置換インドール類の合成2012

    • Author(s)
      廣谷 功,伊藤 晋,荻原 謙太郎,鵜木 萌,重久 浩樹
    • Organizer
      第42回 複素環化学討論会
    • Place of Presentation
      京都テルサ(京都市)
    • Related Report
      2012 Research-status Report
  • [Remarks] 武蔵野大学 教員情報 廣谷 功

    • URL

      http://gyoseki.musashino-u.ac.jp/msuhp/KgApp?kyoinId=ymiygsoiggo

    • Related Report
      2014 Annual Research Report
  • [Remarks] 武蔵野大学薬学部薬化学研究室

    • URL

      http://www.musashino-u.ac.jp/facilities/pharmacy/yakka.html

    • Related Report
      2013 Research-status Report
  • [Remarks] 武蔵野大学薬学部教員情報 廣谷 功

    • URL

      http://gyoseki.musashino-u.ac.jp/msuhp/KgApp?kyoinId=ymiygsoiggo

    • Related Report
      2013 Research-status Report
  • [Remarks] 薬化学研究室

    • URL

      http://www.musashino-u.ac.jp/facilities/pharmacy/yakka.html

    • Related Report
      2012 Research-status Report

URL: 

Published: 2013-05-31   Modified: 2019-07-29  

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