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Development of New Nitrogen-based Ligands for Asymmetric Reactions with Highly Active Catalysts

Research Project

Project/Area Number 15H03808
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionNagoya Industrial Science Research Institute (2016-2017)
Nagoya University (2015)

Principal Investigator

NISHIYAMA HISAO  公益財団法人名古屋産業科学研究所, 研究部, 研究員 (40135421)

Co-Investigator(Kenkyū-buntansha) 伊藤 淳一  名古屋大学, 工学研究科, 講師 (20402480)
Project Period (FY) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000)
Fiscal Year 2017: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2016: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2015: ¥7,280,000 (Direct Cost: ¥5,600,000、Indirect Cost: ¥1,680,000)
Keywords有機合成 / 不斉合成 / 触媒 / 有機金属化学 / 光学活性化合物 / 合成化学 / 触媒化学 / 計算化学
Outline of Final Research Achievements

In organic synthesis, it is important to develop new catalytic reaction providing useful optically active compounds. We have developed new nitrogen-based multidentate ligands for asymmetric catalysis. As N,C,N-type or N,N,O-type ligands, bis(oxazolinyl)phenyl or binaphthol-phenanthroline derivatives were examined to show high stereoselectivity and enantioselectivity for asymmetric conjugate silylation of substituted cyclohexadienones, conjugate addition and susequent alkylation, α-oxidation of oxindole skeleton etc., in the combination with a variety of metals. Plausible catalytic cycles including intermediate or transition state were examined by theoretical calculation to give the corresponding structures for asymmetric conjugate hydrosilylation.

Report

(4 results)
  • 2017 Annual Research Report   Final Research Report ( PDF )
  • 2016 Annual Research Report
  • 2015 Annual Research Report
  • Research Products

    (21 results)

All 2018 2017 2016 2015 Other

All Journal Article (12 results) (of which Peer Reviewed: 12 results,  Open Access: 2 results,  Acknowledgement Compliant: 10 results) Presentation (8 results) (of which Int'l Joint Research: 3 results,  Invited: 1 results) Remarks (1 results)

  • [Journal Article] Design of bifunctional chiral phenanthroline ligand with Lewis basic site for palladium-catalyzed asymmetric allylic substitution2018

    • Author(s)
      Yuki Naganawa, Hiroki Abe, Hisao Nishiyama
    • Journal Title

      Chem. Commun.

      Volume: 54 Issue: 21 Pages: 2674-2677

    • DOI

      10.1039/c8cc00754c

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Desymmetrization of Substituted Cyclohexadienones by Rhodium-Catalyzed Conjugate Hydrosilylation and Theoretical Calculation of Its Mechanistic Aspects2017

    • Author(s)
      Yuki Naganawa, Jun-ichi Ito, Mayu Kawagishi, Hisao Nishiyama
    • Journal Title

      Synthesis

      Volume: 49 Issue: 19 Pages: 4448-4460

    • DOI

      10.1055/s-0036-1590873

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cu(II)-catalyzed Enantioselective α-Hydroxylation and α-Chlorination of β-Ketoesters with N,N,O-Tridentate Chiral Phenanthroline Ligand2016

    • Author(s)
      Naganawa, Y.; Aoyama, T.; Kato, K.; Nishiyama, H.
    • Journal Title

      ChemistrySelect

      Volume: 1 Issue: 9 Pages: 1938-1942

    • DOI

      10.1002/slct.201600449

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Nickel(II)-Catalyzed Asymmetric Michael Addition of Oxindoles with Modified N,N,O-Tridentate Chiral Phenanthroline Ligands2016

    • Author(s)
      Naganawa, Y.; Abe, H.; Nishiyama, H.
    • Journal Title

      Synlett

      Volume: 27 Issue: 13 Pages: 1973-1978

    • DOI

      10.1055/s-0035-1561630

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis of NHC-Oxazoline Pincer Complexes of Rh and Ru and Their Catalytic Activity for Hydrogenation and Conjugate Reduction2016

    • Author(s)
      Ito, J.; Sugino, K.; Matsushima, S.; Sakaguchi, H.; Iwata, H.; Ishihara, T.; Nishiyama, H.
    • Journal Title

      Organometallics

      Volume: 35 Issue: 11 Pages: 1885-1894

    • DOI

      10.1021/acs.organomet.6b00239

    • NAID

      120005868223

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Asymmetric Induction at Remote Quaternary Centers of Cyclohexadienones by Rhodium-Catalyzed Conjugate Hydrosilylation2016

    • Author(s)
      Naganawa, Y.; Kawagishi, M.; Ito, J.; Nishiyama, H.
    • Journal Title

      Angewandte Chemie-International Edition

      Volume: 55 Issue: 24 Pages: 6873-6876

    • DOI

      10.1002/anie.201601636

    • NAID

      120005868222

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Asymmetric Three Component Coupling Reaction of Alkyne, Enone, and Aldehyde Catalyzed by Chiral Phebox Ruthenium Catalysts2016

    • Author(s)
      Ubukata, Shino; Ito, Jun-Ichi; Oguri, Ryota; Nishiyama, Hisao
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 81 Issue: 8 Pages: 3347-3355

    • DOI

      10.1021/acs.joc.6b00374

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Enantioselective Direct Alkynylation of Ketones Catalyzed by Chiral CCN Pincer Rh-III Complexes2016

    • Author(s)
      Ito, J.; Ubukata, S.; Muraoka, S.; Nishiyama, H.
    • Journal Title

      Chemistry-a European Journal

      Volume: 22 Issue: 47 Pages: 16801-16804

    • DOI

      10.1002/chem.201603754

    • NAID

      120005971247

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Renovation of Optically Active Phenanthrolines as Powerful Chiral Ligands for Versatile Asymmetric Metal Catalysis2016

    • Author(s)
      Naganawa, Y.; Nishiyama, H.
    • Journal Title

      Chemical Record

      Volume: 16 Pages: 2573-2584

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Cu(II)-catalyzed enantioselective oxygen atom transfer from oxaziridine to oxindole derivatives with chiral phenanthroline2015

    • Author(s)
      Y. Naganawa, T. Aoyama, H. Nishiyama
    • Journal Title

      Org. Biomol. Chem.

      Volume: 13 Issue: 47 Pages: 11499-11506

    • DOI

      10.1039/c5ob01840d

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Zinc-catalyzed Enantioselective Electrophilic Amination of β-Ketocarbonyl Compounds with Axially Chiral Phenanthroline Ligands2015

    • Author(s)
      Y. Naganawa, H. Komatsu, H. Nishiyama
    • Journal Title

      Chem. Lett.

      Volume: 44 Issue: 12 Pages: 1652-1654

    • DOI

      10.1246/cl.150802

    • NAID

      130005112550

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Construction of Chiral Silicon Center via Rh-Catalyzed Enantioselective Intramolecular Hydrosilylation2015

    • Author(s)
      Y. Naganawa, T. Namba, M. Kawagishi, H. Nishiyama
    • Journal Title

      Chem. Eur. J.

      Volume: 21 Issue: 26 Pages: 9319-9322

    • DOI

      10.1002/chem.201501568

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Enantioselective Direct Alkynylation of Ketones Catalyzed by Pincer Rh(III) Complexes2017

    • Author(s)
      J. Ito, S. Muraoka, S. Ubukata, H. Nishiyama
    • Organizer
      The 19th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Syntheis, June 25-29, 2017, ICC JeJu, Jeju, Korea
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Asymmetric Induction at Remote All-carbon Quaternary Centers of Cyclohexadienones by Rhodium-catalyzed Conjugate Hydrosilylation2017

    • Author(s)
      Y. Naganawa, J. Ito, M. Kawagishi, H. Nishiyama
    • Organizer
      The 19th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Syntheis, June 25-29, 2017, ICC JeJu, Jeju, Korea
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 二級アミノ基を有するNCN型、NCNC型ロジウム錯体の合成とキラルスイッチへの応用2016

    • Author(s)
      伊藤淳一、シチ ロキア、西山久雄
    • 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
    • Year and Date
      2016-09-14
    • Related Report
      2016 Annual Research Report
  • [Presentation] 光学活性オキサゾリン配位錯体による触媒的不斉反応の開発2016

    • Author(s)
      西山久雄
    • Organizer
      日本プロセス化学会2016サマーシンポジウム
    • Place of Presentation
      名古屋国際会議場
    • Year and Date
      2016-07-28
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] Asymmetric Induction at γ-Quaternary Centers by Rh-Phebox Catalyzed Conjugate Hydrosilylation2016

    • Author(s)
      Naganawa. Y.; Kawagishi, M.; Nishiyama, H.
    • Organizer
      20th International Symposium on Homogeneous Catalysis
    • Place of Presentation
      Kyoto Terrssa, Kyoto-shi
    • Year and Date
      2016-07-10
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 不斉触媒反応におけるPhebox-Rh触媒の置換基効果2016

    • Author(s)
      麻奥香菜、田丸雅朝、伊藤淳一、西山久雄
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学
    • Year and Date
      2016-03-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] 様々な金属触媒によるカルボニル化合物の不斉求核付加反応に適用可能なキラルフェナントロリン配位子の設計2015

    • Author(s)
      阿部弘規、永縄友規、西山久雄
    • Organizer
      第46回中部化学関係学協会支部連合秋季大会
    • Place of Presentation
      三重大学
    • Year and Date
      2015-11-07
    • Related Report
      2015 Annual Research Report
  • [Presentation] CCN型三座複合配位子を有するルテニウム錯体の合成と反応2015

    • Author(s)
      杉野香奈絵、伊藤淳一、西山久雄
    • Organizer
      第46回中部化学関係学協会支部連合秋季大会
    • Place of Presentation
      三重大学
    • Year and Date
      2015-11-07
    • Related Report
      2015 Annual Research Report
  • [Remarks] publication

    • URL

      http://www.apchem.nagoya-u.ac.jp/06-II-1/nisilab/Publication.html

    • Related Report
      2015 Annual Research Report

URL: 

Published: 2015-04-16   Modified: 2019-03-29  

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