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Inversions in asymmetric conjugate addition reaction of cyclic enones catalyzed by the Cu/NHC-AgX system

Research Project

Project/Area Number 26410127
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionKansai University

Principal Investigator

Sakaguchi Satoshi  関西大学, 化学生命工学部, 教授 (50278602)

Project Period (FY) 2014-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2016: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2014: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Keywords不斉触媒反応 / カルベン配位子 / 共役付加反応 / 銅触媒反応 / 金属錯体 / 錯体触媒 / 立体反転 / アート錯体
Outline of Final Research Achievements

We reported that the chiral (CH2)2-bridged azolium salt bearing hydroxy-amide group or the corresponding N-heterocyclic carbene (NHC)-Ag complex promoted the Cu-catalyzed asymmetric conjugate addition reaction.
Interestingly, the reversal of enantioselectivity was achieved by changing the order of addition of starting materials. When dialkyl zinc was added to THF solution containing CuOTf, NHC-Ag complex (or azolium salt) and enone, the reaction produced the corresponding 1,4-adduct (Method A).
In contrast, the enantioselectivity of the 1,4-addition reaction was reversed when enone was added to the mixture of a Cu(I) salt, NHC-Ag complex and dialkyl zinc (Method B).

Report

(5 results)
  • 2017 Annual Research Report   Final Research Report ( PDF )
  • 2016 Research-status Report
  • 2015 Research-status Report
  • 2014 Research-status Report
  • Research Products

    (41 results)

All 2018 2017 2016 2015 2014 Other

All Journal Article (6 results) (of which Peer Reviewed: 6 results,  Acknowledgement Compliant: 5 results) Presentation (33 results) (of which Int'l Joint Research: 4 results,  Invited: 1 results) Remarks (2 results)

  • [Journal Article] Inversions in asymmetric conjugate addition reaction of cyclic enones catalyzed by the Cu/NHC-AgX system: Factors affecting the stereoselective formation of both enantiomers2017

    • Author(s)
      Y. Nakano, S. Sakaguchi
    • Journal Title

      J. Organomet. Chem.

      Volume: 876 Pages: 407-416

    • DOI

      10.1016/j.jorganchem.2017.07.025

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Chiral N-heterocyclic carbene iridium catalyst for the enantioselective hydrosilane reduction of ketones2016

    • Author(s)
      Y. Manabe, K. Shinohara, H. Nakamura, H. Teramoto, S. Sakaguchi
    • Journal Title

      J. Mol. Cat. A: Chem.

      Volume: 421 Pages: 138-145

    • DOI

      10.1016/j.molcata.2016.05.020

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Enantioselectivity switch in copper-catalyzed conjugate addition reactions under the influence of a chiral N-heterocyclic carbene-silver complex2016

    • Author(s)
      K. Matsumoto, Y. Nakano, N. Shibata, S. Sakaguchi
    • Journal Title

      RCS Adv.

      Volume: 6 Issue: 10 Pages: 7755-7759

    • DOI

      10.1039/c5ra25926f

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Enantioselective Hydrosilylation of Ketones Catalyzed by a Readily Accessible N-Heterocyclic Carbene-Ir Complex at Room Temperature2014

    • Author(s)
      K. Shinohara, S. Kawabata, H. Nakamura, Y. Manabe, S. Sakaguchi
    • Journal Title

      Eur. J. Org. Chem.

      Volume: 2014 Issue: 25 Pages: 5532-5539

    • DOI

      10.1002/ejoc.201402279

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] C2-symmetric functionalized azolium salt from serine ester for Cu-catalyzed asymmetric conjugate addition reaction2014

    • Author(s)
      J. Kondo, A. Harano, K. Dohi, S. Sakaguchi
    • Journal Title

      J. Mol. Cat. A: Chem.

      Volume: 395 Pages: 66-71

    • DOI

      10.1016/j.molcata.2014.08.006

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Cu-catalyzed asymmetric conjugate addition of dialkylzincs to enones using (±)-trans-1,2-cyclohexanediamine-based bis(NHC) derived from L-leucinol2014

    • Author(s)
      S. Kamihigashi, N. Shibata, S. Sakaguchi
    • Journal Title

      Synlett

      Volume: 25 Issue: 20 Pages: 2933-2937

    • DOI

      10.1055/s-0034-1378916

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] [Ir(cod)2]BF4/アゾリウム触媒系によるケトンのエナンチオ選択的還元反応2018

    • Author(s)
      角山 竜樹,寺本 広,坂口 聡
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] メリフィールド樹脂連結型アゾリウムによる不均一系Ir触媒不斉ヒドロシリル化反応2018

    • Author(s)
      林 大悟,楠本 巧,坂口 聡
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Pd/アゾリウム触媒系によるアリル位置換反応:配位子上のN置換基の違いによる立体選択性のスイッチング2018

    • Author(s)
      福本 香菜,奥野 愛,坂口 聡
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] アゾリウムのN原子上の置換基によって制御されたヒドロキシアミド置換アゾリウム塩と酸化銀の反応2018

    • Author(s)
      上口 恭平,福本 香菜,坂口 聡
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] ヒドロキシアミド置換NHC 前駆体を用いるCu触媒共役付加反応:立体選択性反転のコントロール因子2018

    • Author(s)
      清水 誠生,中野 佑紀,坂口 聡
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] キラルなBis(NHC)配位子前駆体の合成とエナンチオ選択的Cu触媒共役付加反応2018

    • Author(s)
      高橋 菜摘,岩井 優樹,坂口 聡
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Asymmetric Hydrosilylation of Ketone Catalyzed by Cationic Ir Complex In the Presence of Chiral Azolium Salt2017

    • Author(s)
      H. Teramoto, S. Sakaguchi
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大学日吉キャンパス (神奈川県)
    • Related Report
      2016 Research-status Report
  • [Presentation] Cu-catalyzed Asymmetric Conjugate Addition Reaction Under the Influence of 1,2-Cyclohexanediamine-based Azolium Salt2017

    • Author(s)
      Y. Iwai, S. Sakaguchi
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大学日吉キャンパス (神奈川県)
    • Related Report
      2016 Research-status Report
  • [Presentation] Reversal of Enantioselectivity on N-Heterocyclic Carbene-Cu-Catalyzed Conjugate Addition Reaction2016

    • Author(s)
      Y. Nakano, S. Sakaguchi
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学京田辺キャンパス (京都府)
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Hydrosilylation of Ketone Using Cationic Ir Catalyst Precursor: Utilization of Chiral Azolium Salt without Base2016

    • Author(s)
      H. Teramoto, S. Sakaguchi
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学京田辺キャンパス (京都府)
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Ir-Catalyzed Asymmetric Hydrosilylation of Ketone Using N-Heterocyclic Carbene Linked with Merrifield Resin2016

    • Author(s)
      T. Kusumoto, S. Sakaguchi
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学京田辺キャンパス (京都府)
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Enantioselective Transfer Hydrogenation of Diaryl Ketones Using Rhodium or Ruthenium Catalyst2016

    • Author(s)
      R. Kato, R. Takeuchi, S. Sakaguchi
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学京田辺キャンパス (京都府)
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] メリフィールド樹脂と結合したN-ヘテロサイクリックカルベン-イリジウム錯体の調製と不斉触媒反応への利用2016

    • Author(s)
      楠本 巧,坂口 聡
    • Organizer
      第5回JACI/GSCシンポジウム
    • Place of Presentation
      ANAクラウンプラザホテル神戸 (兵庫県)
    • Related Report
      2016 Research-status Report
  • [Presentation] Enantiodivergent Conjugate Addition Reaction Catalyzed by Cu/NHC-Ag System2016

    • Author(s)
      Y. Nakano, S. Sakaguchi
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      早稲田大学西早稲田キャンパス (東京都)
    • Related Report
      2016 Research-status Report
  • [Presentation] Asymmetric Hydrosilylation of Ketone Catalyzed by Cationic Ir Catalyst Precursor Combined with Chiral Azolium Salt2016

    • Author(s)
      H. Teramoto, S. Sakaguchi
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      早稲田大学西早稲田キャンパス (東京都)
    • Related Report
      2016 Research-status Report
  • [Presentation] Catalytic Asymmetric Conjugate Addition Reaction Using Bis(NHC) Ligand: Switching of Stereoselectivity Controlled by Anionic Ligand on Cu Salt2016

    • Author(s)
      Y. Iwai, S. Sakaguchi
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      早稲田大学西早稲田キャンパス (東京都)
    • Related Report
      2016 Research-status Report
  • [Presentation] Cu-Catalyzed Conjugate Addition Reaction with NHC-Ag Complex Allowing Access to Either Enantiomer at will2016

    • Author(s)
      Y. Nakano, S. Sakaguchi
    • Organizer
      International Symposium on Catalysis and Fine Chemicals 2016 (C&FC 2016)
    • Place of Presentation
      台北,台湾
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] N-ヘテロサイクリックカルベン-Ir触媒を用いるケトンの不斉ヒドロシリル化反応2015

    • Author(s)
      眞鍋芳樹,坂口 聡
    • Organizer
      兵庫県立大学Cat-on-cat 新規表面反応研究センター シンポジウム2015
    • Place of Presentation
      姫路・西はりま地場産業センター (兵庫県)
    • Year and Date
      2015-12-10
    • Related Report
      2015 Research-status Report
  • [Presentation] Switching of Enantioselectivity in Cu-Catalyzed 1,4-Addition Reaction Under Influence of Chiral NHC-Ag Complex2015

    • Author(s)
      Y. Nakano, K. Matsumoto, S. Sakaguchi
    • Organizer
      13th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-13)
    • Place of Presentation
      リーガロイヤルホテル京都 (京都府)
    • Year and Date
      2015-11-09
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Enantioselective Hydrosilylation of Ketone Catalyzed by Hydroxyamide Functionalized NHC-Ir Species2015

    • Author(s)
      Y. Manabe, S. Sakaguchi
    • Organizer
      13th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-13)
    • Place of Presentation
      リーガロイヤルホテル京都 (京都府)
    • Year and Date
      2015-11-09
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] ヒドロキシアミド官能基化されたNHC-Ir触媒による ケトンのエナンチオ選択的ヒドロシリル化反応2015

    • Author(s)
      眞鍋芳樹,坂口 聡
    • Organizer
      第116回触媒討論会
    • Place of Presentation
      三重大学 (三重県)
    • Year and Date
      2015-09-16
    • Related Report
      2015 Research-status Report
  • [Presentation] ロイシンならびに1,2-シクロヘキサンジアミンからのアゾリウム塩の調製: Cu触媒不斉共役付加反応2015

    • Author(s)
      石橋 亜津紗,坂口 聡
    • Organizer
      第62回有機金属化学討論会
    • Place of Presentation
      関西大学吹田キャンパス (大阪府)
    • Year and Date
      2015-09-07
    • Related Report
      2015 Research-status Report
  • [Presentation] キラルなNHC-Ag錯体の調製: 触媒的不斉共役付加反応における立体選択性の反転2015

    • Author(s)
      中野 佑紀, 坂口 聡
    • Organizer
      第62回有機金属化学討論会
    • Place of Presentation
      関西大学吹田キャンパス (大阪府)
    • Year and Date
      2015-09-07
    • Related Report
      2015 Research-status Report
  • [Presentation] Highly tunable chiral N-heterocyclic carbene iridium catalyst for enantioselective hydrosilane reduction of ketone2015

    • Author(s)
      S. Sakaguchi, Y. Manabe
    • Organizer
      17th International Symposium on Relations between Homogeneous and Heterogeneous Catalysis Conference (ISHHC17)
    • Place of Presentation
      Utrecht University (The Netherlands)
    • Year and Date
      2015-07-12
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Cu触媒1,4-付加反応における反応試薬の仕込み手順の違いによる立体選択性の逆転2015

    • Author(s)
      松本桂太郎、坂口聡
    • Organizer
      日本化学会 第95春季年会
    • Place of Presentation
      日大船橋キャンパス (千葉県)
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Research-status Report
  • [Presentation] キラルなNHC-Ir錯体触媒を用いるジアリールケトンのエナンチオ選択的ヒドロシリル化反応2015

    • Author(s)
      眞鍋芳樹、坂口聡
    • Organizer
      日本化学会 第95春季年会
    • Place of Presentation
      日大船橋キャンパス (千葉県)
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Research-status Report
  • [Presentation] 金属触媒反応における置換N-ヘテロサイクリックカルベン配位子の開発2015

    • Author(s)
      坂口聡
    • Organizer
      有機金属部会平成26年度第4回例会
    • Place of Presentation
      大阪科学技術センター (大阪府)
    • Year and Date
      2015-01-27
    • Related Report
      2014 Research-status Report
    • Invited
  • [Presentation] ヒドロキシアミド置換されたN-ヘテロサイクリックカルベン-Pd錯体触媒を用いた立体選択的アリル位置換反応2014

    • Author(s)
      奥野愛、坂口聡
    • Organizer
      Cat-on-Cat Symposium in Himeji 2014
    • Place of Presentation
      姫路じばさんビル (兵庫県)
    • Year and Date
      2014-12-13
    • Related Report
      2014 Research-status Report
  • [Presentation] ヒドロキシ基をサイドアームにもつベンズイミダゾリウム塩を用いるCu触媒不斉共役付加反応2014

    • Author(s)
      川島寛正、坂口聡
    • Organizer
      Cat-on-Cat Symposium in Himeji 2014
    • Place of Presentation
      姫路じばさんビル (兵庫県)
    • Year and Date
      2014-12-13
    • Related Report
      2014 Research-status Report
  • [Presentation] 触媒反応系中で発生したNHC-Ir錯体を用いるケトンの不斉ヒドロシリル化反応2014

    • Author(s)
      真鍋芳樹、坂口聡
    • Organizer
      第61回有機金属化学討論会
    • Place of Presentation
      九大病院キャンパス (福岡県)
    • Year and Date
      2014-09-23 – 2014-09-25
    • Related Report
      2014 Research-status Report
  • [Presentation] 官能基化されたアゾリウム塩存在下Cu触媒不斉共役付加反応における立体選択性のスイッチング2014

    • Author(s)
      松本桂太郎、坂口聡
    • Organizer
      第61回有機金属化学討論会
    • Place of Presentation
      九大病院キャンパス (福岡県)
    • Year and Date
      2014-09-23 – 2014-09-25
    • Related Report
      2014 Research-status Report
  • [Presentation] Stereoselective Hydrosilylation of Ketone Catalyzed by in Situ Generated NHC-Ir Species2014

    • Author(s)
      Y. Manabe, S. Sakaguchi
    • Organizer
      XXVI International Conference on Organometallic Chemistry (ICOMC2014)
    • Place of Presentation
      Royton Sapporo (北海道)
    • Year and Date
      2014-07-13 – 2014-07-18
    • Related Report
      2014 Research-status Report
  • [Presentation] Reversal of Enantioselectivity on Cu-catalyzed Asymmetric Conjugate Addition Using Ethylene-bridged, Hydroxy-amide Functionalized Azolium Salt2014

    • Author(s)
      K. Matsumoto, S. Sakaguchi
    • Organizer
      XXVI International Conference on Organometallic Chemistry (ICOMC2014)
    • Place of Presentation
      Royton Sapporo (北海道)
    • Year and Date
      2014-07-13 – 2014-07-18
    • Related Report
      2014 Research-status Report
  • [Remarks] 関西大学化学生命工学部化学・物質工学科 有機化学反応研究室

    • URL

      http://orgchem.chemmater.kansai-u.ac.jp/index.html

    • Related Report
      2017 Annual Research Report
  • [Remarks] 関西大学有機化学反応研究室

    • URL

      http://orgchem.chemmater.kansai-u.ac.jp/

    • Related Report
      2016 Research-status Report 2015 Research-status Report 2014 Research-status Report

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Published: 2014-04-04   Modified: 2019-03-29  

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