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Advanced Molecular Transformations by Development of Chiral Organosuperbase Catalysts

Research Project

Project/Area Number 24350045
Research Category

Grant-in-Aid for Scientific Research (B)

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

Principal Investigator

TERADA Masahiro  東北大学, 理学(系)研究科(研究院), 教授 (50217428)

Project Period (FY) 2012-04-01 – 2016-03-31
Project Status Completed (Fiscal Year 2015)
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不斉合成 / 有機分子触媒 / 水素結合 / 塩基 / 触媒 / 分子認識 / 物質変換 / 反応場
Outline of Final Research Achievements

The development of much stronger organobase is highly demanded to overcome intrinsic limitation of applicable pro-nucleophiles which have relatively acidic proton at the alpha-position, such as 1,3-dicarbonyl compounds and nitroalkanes. In general, the basicity of the organobases increases with increasing the resonance stability of their conjugate acids, the protonated form of the organobases. For instance, introduction of phosphazene or guanidine subunit(s) to the iminophosphorane core stabilizes its conjugate acid, aminophosphonium cation, to afford a series of phosphazene organosuperbases. However, the iminophosphorane modified by the additional phosphazene or guanidine subunit has never been applied to develop chiral organosuperbase so far. We hence designed a pseudo C2-symmetric P3-phosphazen and bis(guanidino)iminophosphorane as a novel family of chiral phosphazene organosuperbases and successfully developed these molecules.

Report

(4 results)
  • 2015 Final Research Report ( PDF )
  • 2014 Annual Research Report
  • 2013 Annual Research Report
  • 2012 Annual Research Report
  • Research Products

    (21 results)

All 2016 2015 2013 2012 Other

All Journal Article (9 results) (of which Peer Reviewed: 9 results,  Acknowledgement Compliant: 3 results,  Open Access: 3 results) Presentation (5 results) (of which Int'l Joint Research: 2 results,  Invited: 4 results) Book (1 results) Remarks (6 results)

  • [Journal Article] Construction of Vicinal Quaternary Stereogenic Centers by Enantioselective Direct Mannich-Type Reaction Using a Chiral Bis(guanidino)iminophosphorane Catalyst2016

    • Author(s)
      Tadahiro Takeda, Azusa Kondoh, and Masahiro Terada
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 55 Issue: 15 Pages: 4734-4737

    • DOI

      10.1002/anie.201601352

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Enantioselective Addition of a 2-Alkoxycarbonyl-1,3-dithiane to Imines Catalyzed by a Bis(guanidino)iminophosphorane Organosuperbase2015

    • Author(s)
      Azusa Kondoh, Masafumi Oishi, Tadahiro Takeda, Masahiro Terada
    • Journal Title

      Angewandte Chemie International Eddition

      Volume: 54 Issue: 52 Pages: 15836-15839

    • DOI

      10.1002/anie.201508178

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ring Expansion of Epoxides under Bronsted Base Catalysis: Formal [3+2] Cycloaddition of β,γ-Epoxy Esters with Imines Providing 2,4,5-Trisubstituted 1,3-Oxazolidines2015

    • Author(s)
      Azusa Kondoh, Kenta Odaira, Masahiro Terada
    • Journal Title

      Angewandte Chemie International Eddition

      Volume: 54 Issue: 38 Pages: 11240-11244

    • DOI

      10.1002/anie.201505893

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Intermediary P3 Phosphazenium Framework and Its Derivatization to Chiral Cationic Macrocycles Including Two P3 Phosphazenium Units with Hydrogen Bond Donor Sites2015

    • Author(s)
      Masahiro Terada, Kengo Goto, Takashi Ikehara, Azusa Kondoh
    • Journal Title

      Heterocycles

      Volume: 90 Issue: 2 Pages: 1396-1404

    • DOI

      10.3987/com-14-s(k)98

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Design and Synthesis of Helically Chiral Spirocyclic P3 Phosphazenes and Characterization of Their Onium Salts2013

    • Author(s)
      M. Terada, K. Goto, M. Oishi, T. Takeda, E. Kwon, A. Kondoh
    • Journal Title

      Synlett

      Volume: 24 Issue: 19 Pages: 2531-2534

    • DOI

      10.1055/s-0033-1340058

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Development of a Chiral Bis(guanidino)iminophosphorane as an Uncharged Organosuperbase for the Enantioselective Amination of Ketones2013

    • Author(s)
      T. Takeda, M. Terada
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 135 Issue: 41 Pages: 15306-15309

    • DOI

      10.1021/ja408296h

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Phosphazene-Catalyzed Intramolecular Cyclization of Nitrogen-Tethered Alkynyl Esters2013

    • Author(s)
      A. Kondoh, K. Ando, M. Terada
    • Journal Title

      Chem. Commun.

      Volume: 49 Issue: 87 Pages: 10254-10256

    • DOI

      10.1039/c3cc46100a

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Guanidine/Azole Binary System as an Efficient Catalyst for Morita-Baylis-Hillman Reaction2012

    • Author(s)
      M. Terada, S. Fukuchi, K. Amagai, M. Nakano, H. Ube
    • Journal Title

      ChemCatChem

      Volume: 4 Issue: 7 Pages: 963-967

    • DOI

      10.1002/cctc.201200149

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Unsymmetrically Substituted 2,2' -Dihydroxy-1,1'-biaryl Derivatives Using Organic-Base-Catalyzed Ferrier-Type Rearrangement as the Key Step2012

    • Author(s)
      M. Terada, K. Dan
    • Journal Title

      Chem. Commum.

      Volume: 48 Issue: 46 Pages: 5781-5783

    • DOI

      10.1039/c2cc31594g

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Presentation] New Aspect of Organosuperbase Catalyst2015

    • Author(s)
      Masahiro Terada
    • Organizer
      Perspectives on Synthetic Organic Chemistry
    • Place of Presentation
      Singapore
    • Year and Date
      2015-09-30
    • Related Report
      2014 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Development of Chiral Bis(guanidino)iminophosphorane as Uncharged Organosuperbase Catalyst for2015

    • Author(s)
      Masahiro Terada
    • Organizer
      IUPAC World Chemistry Congress 2015 Molecular Synthesis Symposia
    • Place of Presentation
      Busan, Korea
    • Year and Date
      2015-08-09
    • Related Report
      2014 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Enantioselective Carbon-Carbon Bond Forming Reactions Catalyzed by Chiral Phosphoric Acids2013

    • Author(s)
      M. Terada
    • Organizer
      Beijing Symposium 2013 on “New Frontiers in Organic Chemistry: New Reagents, New Reactions”
    • Place of Presentation
      Beijing, China
    • Year and Date
      2013-10-09 – 2013-10-12
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Chiral Phosphoric Acids as Versatile Catalysts for Enantioselective Transformations2013

    • Author(s)
      M. Terada
    • Organizer
      The 23rd French-Japanese Symposium on Medicinal and Fine Chemistry
    • Place of Presentation
      Nagasaki, Japan
    • Year and Date
      2013-05-12 – 2013-05-15
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] 水素結合を戦略的相互作用とする有機子触媒の創製2012

    • Author(s)
      寺田眞浩
    • Organizer
      第102回有機合成シンポジウム
    • Place of Presentation
      東京(招待講演)
    • Year and Date
      2012-11-09
    • Related Report
      2012 Annual Research Report
  • [Book] Asymmetric Synthesis II (Asymmetric C-C Bond Formation Using Chiral Guanidine Catalysts)2012

    • Author(s)
      M. Terada
    • Publisher
      Wiley-VCH
    • Related Report
      2012 Annual Research Report
  • [Remarks] 新学術領域研究「有機分子触媒による未来型分子変換」ホームページ

    • URL

      http://www.organocatalysis.jp/

    • Related Report
      2014 Annual Research Report
  • [Remarks] 東北大学 大学院理学研究科 化学専攻 反応有機化学研究室 ホームページ

    • URL

      http://www.orgreact.sakura.ne.jp/index.html

    • Related Report
      2014 Annual Research Report
  • [Remarks] 新学術領域研究「有機分子触媒による未来型分子変換」領域HP

    • URL

      http://www.organocatalysis.jp/

    • Related Report
      2013 Annual Research Report
  • [Remarks] 東北大学・大学院理学研究科・化学専攻・反応有機化学研究室HP

    • URL

      http://www.orgreact.sakura.ne.jp/index.html

    • Related Report
      2013 Annual Research Report
  • [Remarks] 新学術領域研究「有機分子触媒による未来型分子変換」領域HP

    • URL

      http://www.organocatalysis.jp/

    • Related Report
      2012 Annual Research Report
  • [Remarks] 東北大学・大学院理学研究科・化学専攻・反応有機化学研究室HP

    • URL

      http://www.orgreact.sakura.ne.jp/index.html

    • Related Report
      2012 Annual Research Report

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

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