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Solid-Phase Synthesis of Chiral Silicon-Based Reagents and Their Application to Organic Synthesis

Research Project

Project/Area Number 14205126
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionKyoto University

Principal Investigator

SUGINOME Michinori  Kyoto University, Graduate School of Engineering, Professor, 工学研究科, 教授 (60252483)

Project Period (FY) 2002 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥43,160,000 (Direct Cost: ¥33,200,000、Indirect Cost: ¥9,960,000)
Fiscal Year 2004: ¥10,920,000 (Direct Cost: ¥8,400,000、Indirect Cost: ¥2,520,000)
Fiscal Year 2003: ¥13,130,000 (Direct Cost: ¥10,100,000、Indirect Cost: ¥3,030,000)
Fiscal Year 2002: ¥19,110,000 (Direct Cost: ¥14,700,000、Indirect Cost: ¥4,410,000)
KeywordsOptically Active Allylsilane / Alkenylborane / Catalytic Asymmetric Synthesis / Asymmetric Addition Reaction / Enantio-face Selective Reaction / Boron Compounds / Silicon Compounds / Palladium Catalyst / 不斉合成 / アリルシラン / ビスシリル化 / 環化
Research Abstract

New synthetic intermediates and reagents for organic synthesis have been developed in response to the demands for the efficient construction of large chemical libraries consisting of optically active organic molecules. The results of this research projects are summarized below.
(1)Polymer-bound optically active allylsilanes were synthesized via palladium-catalyzed solid-phase intramolecular bis-silylation of optically active allylic alcohols. Thus obtained allylsilanes were found to react with electrophiles, giving highly enantioenriched alcohols and cyclic ethers stereoselectively.
(2)Silylboranes react with various unsaturated organic molecules including vinylcyclopropane and terminal allenes, leading to the synthesis of new organic molecules that contain silicon and boron. Enantioface-selective silaboration of terminal allenes has been developed by using chiral phosphine ligands with palladium complexes, affording enantio-enriched 2-borylallysilanes efficiently, which serve as new 2-b … More orylallyllation reagents for the synthesis of functionalized organoboron compounds.
(3)Cyanoboranes were found to add to carbon-carbon triple bonds in the presence of palladium catalysts. The reaction provides a unique access to 2-borlyacrylonitriles, which serves as convenient reagents for the synthesis of highly substituted α,β-unsaturated nitriles.
(4)Aminoboranes serve as new iminium ion generators in organic synthesis. The reagent allows to avoid acidic reaction conditions, which are usually required for the amination reactions that proceed via the formation of iminium ion intermediates. Strecker reaction, Mannich reaction and reductive amination reactions proceed in the presence of aldehydes, nucleophiles, and aminoboranes under non-acidic reaction conditions.
(5)As a related research project, a new screw-sense selective polymerization reaction has been developed Polymerrization of 1,2-diisocyanobenzen derivatives proceeded with optically active arylpalladium(II) complexes, leading to the formation of optically active poly(quinoxaline-2,3-diyl)s. The selectivity reaches >90% screw-sense excesses when structurally well-tuned chiral organopalladium initiators were used. Less

Report

(4 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (40 results)

All 2005 2004 2003 2002 Other

All Journal Article (33 results) Publications (7 results)

  • [Journal Article] Synthesis and Reactions of Cyclic Silylboranes2005

    • Author(s)
      杉野目道紀
    • Journal Title

      Bull.Chem.Soc.Jpn. 78

      Pages: 321-326

    • NAID

      10014366794

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stereoselective Synthesis of Highly Enantioenriched (E)-Allylsilanes by Palladium-Catalyzed Intramolecular Bis-Silylation : 1,3-Chirality Transfer and Enantienrichment via Dimer2005

    • Author(s)
      杉野目道紀
    • Journal Title

      Chem.Eur.J. 11

      Pages: 2954-2965

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synthesis and Structural Analysis of Oligo(naphthalene-2,3-diyl)s2005

    • Author(s)
      木村 隆尚
    • Journal Title

      Bull.Chem.Soc.Jpn. 78

      Pages: 142-146

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Palladium-Catalyzed Addition of Cyanoboranes to Alkynes Leading to Regio- and Stereoselective Synthesis of β-Boryl-α,β-unsaturated Nitriles2005

    • Author(s)
      杉野目道紀
    • Journal Title

      Angew.Chem., Int.Ed. 44

      Pages: 2380-2380

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synthesis and Reactions of Cyclic Silylboranes2005

    • Author(s)
      M.Suginome et al.
    • Journal Title

      Bull.Chem.Soc.Jpn 78

      Pages: 323-326

    • NAID

      10014366794

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stereoselective Synthesis of Highly Enantioenriched (E)-Allylsilanes by Palladium-Catalyzed Intramolecular Bis-Silylation : 1,3-Chirality Transfer and Enantienrichment via Dimer Formation2005

    • Author(s)
      M.Suginome et al.
    • Journal Title

      Chem.Eur.J. 11

      Pages: 2954-2965

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synthesis and Structural Analysis of Oligo(naphthalene-2,3-diyl)s2005

    • Author(s)
      M.Suginome et al.
    • Journal Title

      Bull.Chem.Soc.Jpn. 78

      Pages: 142-146

    • NAID

      10014272029

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Palladium-Catalyzed Addition of Cyanoboranes to Alkynes Leading to Regio-and Stereoselective Synthesis of β-Boryl-α,β-unsaturated Nitriles2005

    • Author(s)
      M.Suginome et al.
    • Journal Title

      Angew.Chem., Int.Ed. 44

      Pages: 2380-3282

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synthesis and Reactions of Cyclic Silylboranes2005

    • Author(s)
      杉野目 道紀
    • Journal Title

      Bull.Chem.Soc.Jpn. 78

      Pages: 323-326

    • NAID

      10014366794

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Stereoselective Synthesis of Highly Enantioenriched (E)-Allylsilanes Palladium-Catalyzed Intramolecular Bis-Silylation : 1,3-Chirality Transfer and Enantienrichment via Dimer Formation2005

    • Author(s)
      杉野目 道紀
    • Journal Title

      Chem.Eur.J. (in press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Synthesis and Structural Analysis of Oligo(naphthalene-2,3-diyl)s2005

    • Author(s)
      伊藤 嘉彦
    • Journal Title

      Bull.Chem.Soc.Jpn. 78

      Pages: 142-146

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Palladium-Catalyzed Addition of Cyanoboranes to Alkynes Leading to Regio- and Stereoselective Synthesis of β-Boryl-α,β-unsaturated Nitriles2005

    • Author(s)
      杉野目 道紀
    • Journal Title

      Angew.Chem. (in press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] New Look at Boron Enolate Chemistry : Aminative C-C Bond Formation Using Diaminoboron Enolate with Aldehyde2004

    • Author(s)
      杉野目道紀
    • Journal Title

      Org.Lett. 6

      Pages: 1167-1169

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Aminoboranes as "Compatible" Iminium Ion Generators in Aminative C-C Bond Formations2004

    • Author(s)
      杉野目道紀
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 13196-13197

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] ポリ(キノキサリン-2,3-ジイル)のらせん構造2004

    • Author(s)
      杉野目道紀
    • Journal Title

      高分子 53

      Pages: 945-945

    • NAID

      10014126054

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] New Look at Boron Enolate Chemistry : Aminative C-C Bond Formation Using Diaminoboron Enolate with Aldehyde2004

    • Author(s)
      M.Suginome et al.
    • Journal Title

      Org.Lett. 6

      Pages: 1167-1169

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Aminoboranes as "Compatible" Iminium Ion Generators in Aminative C-C Bond Formations2004

    • Author(s)
      M.Suginome et al.
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 13196-13197

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Aminoboranes as "Compatible" Iminium Ion Generators in Aminative C-C Bond Formations2004

    • Author(s)
      杉野目 道紀
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 13196-13197

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Palladium- and Nickel-Catalyzed Intramolecular Cyanoboration of Alkynes2003

    • Author(s)
      杉野目道紀
    • Journal Title

      J.Am.Chem.Soc. 125

      Pages: 6358-6539

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Enantioface-Selective Palladium-Catalyzed Silaboration of Allenes via Double Asymmetric Induction2003

    • Author(s)
      杉野目道紀
    • Journal Title

      J.Am.Chem.Soc. 125

      Pages: 11174-11175

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Regio- and stereoselective synthesis of boryl-substituted allylsilanes via transition metalcatalyzed silaboration2003

    • Author(s)
      杉野目道紀
    • Journal Title

      J.Organomet.Chem. 680

      Pages: 43-50

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stereoselective Accesses to Enantioenriched Allyl-, Allenyl-, and Propargylsilanes via Si-Si Bond Activation by Palladium-Isocyanide Catalysts2003

    • Author(s)
      杉野目道紀
    • Journal Title

      J.Organomet.Chem. 685

      Pages: 218-229

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Palladium-and Nickel-Catalyzed Intramolecular Cyanoboration of Alkynes2003

    • Author(s)
      M.Suginome et al.
    • Journal Title

      J.Am.Chem.Soc. 125

      Pages: 6358-6359

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Enantioface-Selective Palladium-Catalyzed Silaboration of Allenes via Double Asymmetric Induction2003

    • Author(s)
      M.Suginome et al.
    • Journal Title

      J.Am.Chem.Soc. 125

      Pages: 11174-11175

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Regio-and stereoselective synthesis of boryl-substituted allylsilanes via transition metal-catalyzed silaboration2003

    • Author(s)
      M.Suginome et al.
    • Journal Title

      J.Organomet.Chem.(Special issue : Frontiers in Boron Chemistry) 680

      Pages: 43-50

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stereoselective Accesses to Enantioenriched Allyl-, Allenyl-, and Propargylsilanes via Si-Si Bond Activation by Palladium-Isocyanide Catalysts2003

    • Author(s)
      M.Suginome et al.
    • Journal Title

      J.Organomet.Chem.(Special issue : A Half Century of Polysilane Chemistry) 685

      Pages: 218-229

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] 1,2-Azaboretidine Formation in the Reactions of (Boryl)(silyl)iminomethanes via Possible Generation of (Amino)(boryl)carbene Species2002

    • Author(s)
      杉野目道紀
    • Journal Title

      J.Organonmet.Chem. 643-644

      Pages: 508-508

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Nickel-Catalyzed Silaboration of Small-Ring Vinylcycloalkanes : Regio- and Stereoselective (E)-Allylsilane Formation via C-C Bond Cleavage.2002

    • Author(s)
      杉野目道紀
    • Journal Title

      Organometallics 21

      Pages: 1537-1539

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Bis(dialkylamino)cyanoboranes : highly efficient reagents for the Strecker-type aminative cyanation of aldehydes and ketones2002

    • Author(s)
      杉野目道紀
    • Journal Title

      Chem.Comm.

      Pages: 1392-1393

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] ビスメタル化を利用した新規アリルシラン反応剤の精密合成:コンビナトリアルケミストリーとの接点2002

    • Author(s)
      杉野目道紀
    • Journal Title

      有機合成化学協会誌 60

      Pages: 502-503

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] 1,2-Azaboretidine Formation in the Reactions of (Boryl)(silyl)iminomethanes via Possible Generation of (Amino)(boryl)carbene Species2002

    • Author(s)
      M.Suginome et al.
    • Journal Title

      J.Organomet.Chem.(Special issue dedicated to Prof.F.Mathey) 508

      Pages: 643-644

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Nickel-Catalyzed Silaboration of Small-Ring Vinylcycloalkanes : Regio-and Stereoselective (E)-Allylsilane Formation via C-C Bond Cleavage.2002

    • Author(s)
      M.Suginome et al.
    • Journal Title

      Organometallics 21

      Pages: 1537-1539

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Bis(dialkylamino)cyanoboranes : highly efficient reagents for the Strecker-type aminative cyanation of aldehydes and ketones2002

    • Author(s)
      M.Suginome et al.
    • Journal Title

      Chem.Comm.

      Pages: 1392-1393

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Publications] Michinori Suginome: "Regio- and stereoselective synthesis of boryl-substituted allylsilanes via transition metal-catalyzed silaboration"J.Organomet.Chem.. 680. 43-50 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Michinori Suginome: "Stereoselective Accesses to Enantioenriched Allyl-, Allenyl-, and Propargylsilanes via Si-Si Bond Activation by Palladium-Isocyanide Catalysts"J.Organomet.Chem.. 685. 218-229 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Michinori Suginome: "Enantio-selective Palladium-Catalyzed Silaboration of Allenes via Double Asymmetric Induction"J.Am.Chem.Soc.. 125・37. 11174-11175 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Michinori Suginome: "Palladium- and Nickel-Catalyzed Intramolecular Cyanoboration of Alkynes"J.Am.Chem.Soc.. 125・16. 6358-6359 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Michinori Suginome: "A New Look at Boron Enolate Chemistry : Aminative C-C Bond Formation Using Diaminoboron Enolate with Aldehyde"Org.Lett.. (in press). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Michinori Suginome: "Regio-and stereoselective synthesis of boryl-substituted allylsilanes via transition metal-catalyzed silaboration"J.Organomet.Chem.. (印刷中). (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Michinori Suginome: "Stereoselective Accesses to Enantioenriched Allyl-, Allenyl-, and Propargylsilanes via Si-Si Bond Activation by Palladium-Isocyanide Catalysts"J.Organomet.Chem.. (印刷中). (2003)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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