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Enantio- and Diastereoselective Cyclopropanation with Halodiazoacetophenone

Research Project

Project/Area Number 26860002
Research Category

Grant-in-Aid for Young Scientists (B)

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

Principal Investigator

TSUBOWA Koji  北海道大学, 薬学研究院, 研究員 (00572497)

Project Period (FY) 2014-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2016: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2015: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2014: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Keywords合成化学 / 不斉触媒反応 / ロジウム(II)錯体
Outline of Final Research Achievements

The transition metal-catalyzed asymmetric cyclopropanation reaction of alkenes with diazo compounds represents one of the most powerful means for the construction of optically active cyclopropane building blocks. Hansen and co-workers developed highly diastereoselective cyclopropanations of alkenes with halodiazoacetates, but the asymmetric induction was below 10% ee.
The cyclopropanation with bromodiazoacetophenone under catalysis by Rh2(S-TBPTTL)4 produced cis-cyclopropene product in 75% yield with 85% ee. In addition, it was found that the reaction with chlorodiazoacetophenone afforded the corresponding cyclopropene with 91% ee.

Report

(4 results)
  • 2016 Annual Research Report   Final Research Report ( PDF )
  • 2015 Research-status Report
  • 2014 Research-status Report
  • Research Products

    (17 results)

All 2017 2016 2015 2014 Other

All Journal Article (2 results) (of which Peer Reviewed: 2 results,  Acknowledgement Compliant: 2 results) Presentation (10 results) (of which Int'l Joint Research: 2 results) Remarks (5 results)

  • [Journal Article] Diastereo- and Enantioselective Construction of 6,7-Dioxabicyclo[2.2.1]heptane Derivatives by a Dirhodium(II)-Catalyzed Intramolecular C-H Insertion Reaction2017

    • Author(s)
      Miyazawa, T.; Imai, K.; Ito, M.; Takeda, K.; Anada, M.; Matsunaga, S.; Hashimoto, S.
    • Journal Title

      Heterocycles

      Volume: 95 Issue: 2 Pages: 1211-1229

    • DOI

      10.3987/com-16-s(s)72

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Diastereo- and enantioselective intramolecular 1,6-C-H insertion reactions of α-diazo esters catalyzed by chiral dirhodium(II) carboxylates2015

    • Author(s)
      Ito, M.; Kondo, Y.; Nambu, H.; Anana, M.; Takeda, K.; Hashimoto, S.
    • Journal Title

      Tetrahedron Lett.

      Volume: 56 Issue: 11 Pages: 1397-1400

    • DOI

      10.1016/j.tetlet.2015.01.125

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] 二核ロジウム(II)カルボキシラート錯体を用いた α-ジアゾエステルの分子内不斉C-H挿入反応2016

    • Author(s)
      宮澤拓, 南和志, 今井こずえ, 竹田幸司, 穴田仁洋, 松永茂樹, 橋本俊一
    • Organizer
      日本薬学会 第136年会
    • Place of Presentation
      パシフィコ横浜(神奈川県横浜市)
    • Year and Date
      2016-03-29
    • Related Report
      2015 Research-status Report
  • [Presentation] Enantio- and diastereoselective intramolecular C-H insertion of α-diazoesters catalyzed by chiral dirhodium(II) carboxylates2015

    • Author(s)
      Taku Miyazawa, Kazushi Minami, Kozue Imai, Koji Takeda, Masahiro Anada, Shigeki Matsunaga, Shunichi Hashimoto
    • Organizer
      Pacifichem 2015
    • Place of Presentation
      Hawaii Convention Center (Honolulu, Hawaii, USA)
    • Year and Date
      2015-12-16
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Dirhodium(II) complex-catalyzed enantioselective carbonyl ylide cycloaddition reactions under continuous flow conditions2015

    • Author(s)
      Koji Takeda, Akihito Hirota, Masahiro Anada, Shunichi Hashimoto
    • Organizer
      Pacifichem 2015
    • Place of Presentation
      Hawaii Convention Center (Honolulu, Hawaii, USA)
    • Year and Date
      2015-12-16
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Rh(II)カルボキシラート錯体を用いたアリールジアゾアセタートの分子内不斉シクロプロパン化反応2015

    • Author(s)
      滋野大喜, 竹田幸司, 穴田仁洋, 松永茂樹, 橋本俊一
    • 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11月ホール(大阪府東大阪市)
    • Year and Date
      2015-10-26
    • Related Report
      2015 Research-status Report
  • [Presentation] ロジウム(II)カルボキシラート錯体を用いたハロジアゾアセタートの分子間不斉シクロプロパン化反応2015

    • Author(s)
      小林優貴,高坂祐平,穴田仁洋,竹田幸司,橋本俊一
    • Organizer
      日本薬学会第135年会
    • Place of Presentation
      神戸
    • Year and Date
      2015-03-25 – 2015-03-28
    • Related Report
      2014 Research-status Report
  • [Presentation] ロジウム(II)カルボキシラート錯体を用いたアリールジアゾアセタートの分子内不斉シクロプロパン化反応2015

    • Author(s)
      滋野大喜,竹田幸司,穴田仁洋,橋本俊一
    • Organizer
      日本薬学会第135年会
    • Place of Presentation
      神戸
    • Year and Date
      2015-03-25 – 2015-03-28
    • Related Report
      2014 Research-status Report
  • [Presentation] ロジウム(II)カルボキシラート錯体を用いるα-ジアゾエステルの分子内不斉1,6-C-H挿入反応2015

    • Author(s)
      近藤侑司,伊藤元気,竹田幸司,橋本俊一
    • Organizer
      日本薬学会第135年会
    • Place of Presentation
      神戸
    • Year and Date
      2015-03-25 – 2015-03-28
    • Related Report
      2014 Research-status Report
  • [Presentation] Enantio- and Diastereoselective Intramolecular 1,6-C-H Insertion of α-Diazoesters Catalyzed by Chiral Dirhodium(II) Carboxylates2014

    • Author(s)
      Yuji Kondo, Motoki Ito, Koji Takeda, Shunichi Hashimoto
    • Organizer
      XXVI International Conference on Organometallic Chemistry
    • Place of Presentation
      札幌
    • Year and Date
      2014-07-13 – 2014-07-18
    • Related Report
      2014 Research-status Report
  • [Presentation] Enantio- and Diastereoselective Cyclopropanation with α-Halodiazocarbonyl Compounds2014

    • Author(s)
      Yuki Kobayashi, Meng Lv, Koji Takeda, Shunichi Hashimoto
    • Organizer
      XXVI International Conference on Organometallic Chemistry
    • Place of Presentation
      札幌
    • Year and Date
      2014-07-13 – 2014-07-18
    • Related Report
      2014 Research-status Report
  • [Presentation] α-ハロジアゾカルボニル化合物を用いた不斉シクロプロパン化反応2014

    • Author(s)
      小林優貴,呂夢,竹田幸司,橋本俊一
    • Organizer
      第26回万有札幌シンポジウム
    • Place of Presentation
      札幌
    • Year and Date
      2014-07-05
    • Related Report
      2014 Research-status Report
  • [Remarks] 薬品製造化学研究室 - 北海道大学大学院薬学研究院

    • URL

      http://www.pharm.hokudai.ac.jp/yakuzou/

    • Related Report
      2016 Annual Research Report
  • [Remarks] 北海道大学 薬学部・大学院薬学研究院

    • URL

      http://www.pharm.hokudai.ac.jp

    • Related Report
      2016 Annual Research Report 2015 Research-status Report
  • [Remarks] 北海道大学大学院薬学研究院 薬品製造化学研究室 -

    • URL

      http://www.pharm.hokudai.ac.jp/yakuzou/

    • Related Report
      2015 Research-status Report
  • [Remarks] 北海道大学大学院薬学研究院 薬品製造化学研究室

    • URL

      http://www.pharm.hokudai.ac.jp/yakuzou/hashimotolab/index.html

    • Related Report
      2014 Research-status Report
  • [Remarks] 北海道大学 薬学部・大学院薬学研究院

    • URL

      http://www.pharm.hokudai.ac.jp/

    • Related Report
      2014 Research-status Report

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Published: 2014-04-04   Modified: 2018-03-22  

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