• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Synthetic Chemistry of Allenic Compounds Catalyzed/Mediated by Transition-Metal Species

Research Project

Project/Area Number 24350044
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypePartial Multi-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionHokkaido University

Principal Investigator

OGASAWARA Masamichi  北海道大学, 触媒化学研究センター, 准教授 (70301231)

Project Period (FY) 2012-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥18,460,000 (Direct Cost: ¥14,200,000、Indirect Cost: ¥4,260,000)
Fiscal Year 2014: ¥5,850,000 (Direct Cost: ¥4,500,000、Indirect Cost: ¥1,350,000)
Fiscal Year 2013: ¥5,720,000 (Direct Cost: ¥4,400,000、Indirect Cost: ¥1,320,000)
Fiscal Year 2012: ¥6,890,000 (Direct Cost: ¥5,300,000、Indirect Cost: ¥1,590,000)
Keywordsアレン / 遷移金属触媒 / 軸不斉 / 天然物 / 不斉合成 / 均一系触媒 / パラジウム / 全合成 / 薬理活性 / ビススルホン / 不斉転写
Outline of Final Research Achievements

Synthetic chemistry of allenic compounds, which are important synthones in organic chemistry, has been developed using various transition-metal speceis. It was found that the use of BDT, which is a cyclic bissulfone, as a pronucleophile in the palladium-catalyzed allene synthesis reaction afforded the corresponding axially chiral allenes in high yields with excellent enantioselectivity. This novel reaction conditions enabled us to access various alkyl-substituted allenes, and thus the asymmetric total synthesis of a wide range of naturally occurring allenes could be realized.
Easily accessible 3-bromopenta-2,4-dienyl acetate was applied to the palladium-catalyzed reaction with soft nucleophiles. The reaction proceeded through the stepwise twofold nucleophilic substitution via formal SN2'- and SN2-processes giving the various doubly functionalized C2-symmetric allenes in good yields.

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 2012

All Journal Article (13 results) (of which Peer Reviewed: 13 results,  Acknowledgement Compliant: 1 results) Presentation (8 results) (of which Invited: 7 results)

  • [Journal Article] Simultaneous Induction of Axial and Planar-Chirality in Arene-Chromium Complexes by Molybdenum-Catalyzed Enantioselective Ring-Closing Metathesis2015

    • Author(s)
      K. Kamikawa, S. Arae, W.-Y. Wu, C. Nakamura, T. Takahashi, M. Ogasawara
    • Journal Title

      Chemistry-A European Journal

      Volume: 21 Issue: 13 Pages: 4954-4957

    • DOI

      10.1002/chem.201500226

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Synthesis of Macrocyclic Heterobiaryl Derivatives by Molybdenum-Catalyzed Asymmetric Ring-Closing Metathesis Inducing Winding Vine-Shaped Molecular Asymmetry2015

    • Author(s)
      Y. Okayama, S. Tsuji, Y. Toyomori, T. Mori, S. Arae, W.-Y. Wu, T. Takahashi, M. Ogasawara
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 54 Issue: 16 Pages: 4927-4931

    • DOI

      10.1002/anie.201500459

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Desymmetrization of 1, 2, 3-Trisubstituted Metallocenes by Molybdenum-Catalyzed Asymmetric Intraannular Ring-Closing Metathesis2015

    • Author(s)
      S. Arae, K. Nakajima, T. Takahashi, M. Ogasawara
    • Journal Title

      Organometallics

      Volume: 34 Issue: 7 Pages: 1197-1202

    • DOI

      10.1021/om5011484

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Asymmetric Synthesis of Planar-Chiral Transition-Metal Complexes2015

    • Author(s)
      S. Arae, M. Ogasawara
    • Journal Title

      Tetrahedron Letters

      Volume: 56 Issue: 14 Pages: 1751-1761

    • DOI

      10.1016/j.tetlet.2015.01.130

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hybrid sponge comprised of galactosylated chitosan and hyaluronic acid mediates the co-culture of hepatocytes and endothelial cells2014

    • Author(s)
      Shang, Y., M. Tamai, R. Ishii, N. Nagaoka, Y. Yoshida, M. Ogasawara, J. Yang, Y. Tagawa
    • Journal Title

      J. Biosci. Bioeng.

      Volume: 117 Issue: 1 Pages: 99-106

    • DOI

      10.1016/j.jbiosc.2013.06.015

    • Related Report
      2014 Annual Research Report 2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Phosphine-Olefin Ligands Based on a Planar-Chiral(π-Arene)chromium Scaffold : Design, Synthesis, and Application in Asymmetric Catalysis2014

    • Author(s)
      M. Ogasawara, Y.-Y. Tseng, S. Arae, T. Morita, T. Nakaya, W.-Y. Wu, T. Takahashi, K. Kamikawa
    • Journal Title

      the Journal of the American Chemical Society

      Volume: 136 Issue: 26 Pages: 9377-9384

    • DOI

      10.1021/ja503060e

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Phosphine Oxide-Catalyzed Enantioselective Intramolecular Aldol Reaction via Regioselective Enolization of Unsymmetrical Diketones with Tetrachlorosilane2014

    • Author(s)
      Kotani, S.; Aoki, S.; Sugiura, M.; Ogasawara, M.; Nakajima, M.
    • Journal Title

      Org. Lett.

      Volume: 16 Issue: 18 Pages: 4802-4805

    • DOI

      10.1021/ol502269w

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Kioetio Resolution of Planar-Chiral,1,2-Disuhsrituted Fetroones by Molybdenum-Caralyzed Asymmetric Iutraanular Ring-Cloeing Metafhesis2013

    • Author(s)
      Masamichi Ogasawara, Sachie Arae, Susumu Watanabe, Kiyohiko Nakajima, Tamotsu Takahashi
    • Journal Title

      Chemistry-A European Journel

      Volume: 19 Issue: 13 Pages: 4151-4154

    • DOI

      10.1002/chem.201300116

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Characterization of Benzo[b]phosphaferrocene Derivatives2013

    • Author(s)
      Ogasawara, Masamichi; Arae, Sachie; Watanabe, Susumu; Subbarayan, Velusamy; Sato, Hiroyasu; Takahashi, Tamotsu
    • Journal Title

      Organometallics

      Volume: 32(17) Issue: 17 Pages: 4997-5000

    • DOI

      10.1021/om400496b

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Inter-versus Intraanular-Ring-Closing Metathesis of Polyallylferrocenes Ftye-Fold RCM within a Single Molecole2013

    • Author(s)
      Masamichi Ogasawara, Wei-Yi Wu, Sachie Arae, Kiyohiko Nakajima, Tamotsu Takahashi
    • Journal Title

      Organometallics

      Volume: 32 Issue: 21 Pages: 6593-6598

    • DOI

      10.1021/om400936b

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Helically Chiral Diene in Asymmetric Catalysis: C2-Symmetric (Z,Z)-2,3-Bis[1-(diphenylphosphinyl)ethylidene]tetralin as Highly Active Lewis-Base Organocatalyst2013

    • Author(s)
      Ogasawara, M.; Kotani, S.; Nakajima, H.; Furusho, H.; Miyasaka, M.; Shimoda, Y.; Wu, W.-Y.; Sugiura, M.; Takahashi, T.; Nakajima, M.
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 52 Issue: 51 Pages: 13798-13802

    • DOI

      10.1002/anie.201308112

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Effects of Silyl Substituents on the Palladium-Catalyzed Asymmetric Synthesis of Axially Chiral (Allenylmethy1)silanes and Their SE2 Chirality Transfer Reactions2012

    • Author(s)
      小笠原正道
    • Journal Title

      European Journal of Organic Chemistry

      Volume: 2012 Issue: 8 Pages: 1656-1663

    • DOI

      10.1002/ejoc.201101634

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Preparation of C2-Symmetric Allenes by Palladium-Catalyzed Double-Nucleophilic Substitution on 3-Bromopenta-2,4-dienyl Acetate2012

    • Author(s)
      小笠原正道
    • Journal Title

      Journal of Organic Chemistry

      Volume: 77 Issue: 12 Pages: 5406-5410

    • DOI

      10.1021/jo300511e

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Presentation] Design, Synthesis, and Application of Atropisomeric Chiral Dienes in Asymmetric Catalysis2014

    • Author(s)
      Masamichi Ogasawara
    • Organizer
      The 8th Singapore International Chemical Conference (SICC8)
    • Place of Presentation
      Singapore (Singapore)
    • Year and Date
      2014-12-14 – 2014-12-17
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] 均一系遷移金属触媒による非中心不斉の立体制御2014

    • Author(s)
      小笠原正道
    • Organizer
      オルガノメタリックセミナー
    • Place of Presentation
      東京農工大学(東京都小金井市)
    • Year and Date
      2014-11-25
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Enantioselective Synthesis of Planar-Chiral Ferrocene-Fused 4-Pyridones and Their Application in Construction of Pyridine-Based Organocatalyst Library2014

    • Author(s)
      Masamichi Ogasawara
    • Organizer
      Vietnam Malaysia International Chemical Conference
    • Place of Presentation
      Hanoi (Vietnam)
    • Year and Date
      2014-11-07 – 2014-11-09
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Development of Enantioselective Transformations on (η6-Arene)chromium Templates by Molybdenum-Catalyzed Asymmetric Metathesis Reactions2014

    • Author(s)
      Masamichi Ogasawara
    • Organizer
      The 18th Malaysian International Chemical Congress
    • Place of Presentation
      Kuala Lumpur (Malaysia)
    • Year and Date
      2014-11-03 – 2014-11-05
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Catalytic Enantioselective Synthesis of Planar-Chiral Transition-Metal Complexes and Their Application in Organic Transformations2014

    • Author(s)
      Masamichi Ogasawara
    • Organizer
      The 8th Asian European Symposium on Metal-Mediated Efficient Organic Synthesis (8th AES-MMEOS)
    • Place of Presentation
      Izmir (Turkey)
    • Year and Date
      2014-09-07 – 2014-09-10
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Development of Catalytic Enantioselective Transformations Utilizing (η6-Arene)chromium Templates and Chiral Molybdenum-Alkylidene Catalysts2014

    • Author(s)
      Masamichi Ogasawara
    • Organizer
      41st International Conference on Coordination Chemistry (ICCC-41)
    • Place of Presentation
      Singapore (Singapore)
    • Year and Date
      2014-07-21 – 2014-07-25
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] alladium-Catalyzed Asymmetric Synthesis of Axially Chiral Allenes and Application to Synthesis of Allenic Natural Products2013

    • Author(s)
      Masamichi Ogasawara
    • Organizer
      The 48th Advances in Organic, Bioorganic and Pharmaceutical Chemistry
    • Place of Presentation
      Harmony Hotel (Spindleruv Mlyn, Czech Republic)
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Asymmetric Total Synthesis of Axially Chiral Naturally Occurring Allenes Utilizing Enantioselective Palladium-Catalyzed Reaction2012

    • Author(s)
      Masamichi Ogasawara, Mayuka Suzuki, Tamotsu Takahashi
    • Organizer
      59th Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      大阪大学(大阪府)
    • Related Report
      2012 Annual Research Report

URL: 

Published: 2012-04-24   Modified: 2019-07-29  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi