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Selective Synthesis through Dehydrogenative Silylation with Optically Active Gold(I) Complex

Research Project

Project/Area Number 18550088
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

ITO Hajime  Hokkaido University, Faculty of Science, Associate Professor (90282300)

Project Period (FY) 2006 – 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥4,120,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥420,000)
Fiscal Year 2007: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2006: ¥2,300,000 (Direct Cost: ¥2,300,000)
KeywordsOrganic Chemistry / Gold(I) Complex / Asymmetric Synthesis / Silylation / Environmentally Benign Catalyst / 合成化学 / 環境技術 / 金触媒
Research Abstract

Efficient synthesis of optically active compounds is important issue in organic synthesis. In addition, development of new reactions for efficient utilization of resources and reduction of wastes have become very important subject. In this study, the new methods involving kinetic resolution of chiral alcohols through dehydrogenative silylation with optically active gold(I) complexes were examined.
As a preliminary experiment, xantphos-type ligands that have different steric bulk were prepared and the gold(I)-catalyzed dehydrogenative silylation with these ligands was studied. The sterically hindered ligands showed high activities. Next, kinetic resolutions of chiral alcohols were tested by using chiral phosphine ligands. Although the optically active alcohols were obtained, the enantiomeric purities of the resultant products were low.
In order to develop more efficient gold(I) catalysts for kinetic resolution, synthesis and characterization of a gold(I) hydride compound, which is expected to be a key intermediate of catalysis, were investigated. Although gold(I) hydride compounds had never been characterized in solution before, the researcher found that the gold hydride secrecies were generated in the gold(I)-catalyzed dehydrogenative silylation of alcohols. The gold(I) hydride species were characterized by H, P, C, NMR and ESI-Mass.

Report

(3 results)
  • 2007 Annual Research Report   Final Research Report Summary
  • 2006 Annual Research Report
  • Research Products

    (49 results)

All 2008 2007 2006

All Journal Article (23 results) (of which Peer Reviewed: 13 results) Presentation (24 results) Patent(Industrial Property Rights) (2 results)

  • [Journal Article] Reversible Mechanochromic Luminescence of[(C_6F_5Au)_2(|-1, 4-diisocyanobenzene)]2008

    • Author(s)
      H. Ito, T. Saito, N. Oshima, N. Kitamura, S. Ishizaka, Y.Hinatsu, M. Wakeshima, M. Kato, K. Tsuge, M. Sawamura
    • Journal Title

      J. Am. Chem. Soc. 130

      Pages: 10044-10045

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Synthesis of Optically Active Boron-Silicon Bifunctional Cyclopropane Derivatives through Enantioselective Copper(I)-Catalyzed Reaction of Allylic Carbonates with a Diboron Derivative2008

    • Author(s)
      H. Ito, Y. Kosaka, K. Nonoyama, Y. Sasaki, M. Sawamura
    • Journal Title

      Angew. Chem., Int. Ed. 47

      Pages: 7424-7427

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Copper-catalyzed Substitution of Allylic Carbonates with Diboron: A New Approach to Allylboronate Synthesis2008

    • Author(s)
      H. Ito, S. Ito, Y. Sasaki, K. Matsuura, M. Sawamura
    • Journal Title

      Pure. Appl. Chem. 80

      Pages: 1039-1045

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Enantioselective Addition of Terminal Alkynes to Aromatic Aldehydes Catalyzed by Cu (I) Complexes with Wide Bite-Angle Chiral Bisphosphine Ligands: Optimization, Scope and Mechanistic Studies2008

    • Author(s)
      Y. Asano, H. Ito, K. Hara, M. Sawamura
    • Journal Title

      Organometallics 27

      Pages: 3901-3904

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] 求核的ホウ素-金属化学種の新展開2008

    • Author(s)
      伊藤 肇
    • Journal Title

      化学と工業 61

      Pages: 224-225

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] 11族金属触媒におけるσ結合メタセシス反応を基軸とする合成反応2008

    • Author(s)
      伊藤 肇
    • Journal Title

      有機合成化学協会誌 66(印刷中)

    • NAID

      10024409748

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Reversible Mechanochromic Luminescence of [(C_6F_5Au)_2(μ-1, 4-diisocyanobenzene)]2008

    • Author(s)
      H. Ito, T. Saito, N. Oshima, N. Kitamura, S. Ishizaka, Y. Hinatsu, M. Wakeshima, M. Kato, K. Tsuge, M. Sawamura
    • Journal Title

      J. Am. Chem. Sac. 130

      Pages: 10044-10045

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Enantioselective Addition of Terminal Alkynes to Aromatic Aldehydes Catalyzed by Cu(I) Complexes with Wide Bite-Angle Chiral Bisphosphine Ligands: Optimization, Scope and Mechanistic Studies2008

    • Author(s)
      Y. Asano, H. Ito, K. Hara, M. Sawamura
    • Journal Title

      Organometallics 27

      Pages: 3901-3904

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] New Aspects of Nucleophilic Boron-Metal Compounds2008

    • Author(s)
      H. Ito
    • Journal Title

      Kagaku to Kogyo 61

      Pages: 224-225

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] New Catalytic Reactions of Group 1I Metal Complexes through a-Bond Metathesis2008

    • Author(s)
      H. Ito
    • Journal Title

      J. Synth. Org. Chem. Jpn 66(In press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Synthesis and Sruchural Characterization of a Tetranuclear Platinum (II) Metallamacrocycle Containing 1, 3-Diisocyanoarene Ligands2007

    • Author(s)
      H. Ito, T. Maeda, M. Sawamura
    • Journal Title

      Bull. Chem. Soc. Jpn. 80

      Pages: 1981-1986

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Design and Synthesis of Isocyanide Ligands for Catalysis: Application to Rh-Catalyzed Hydrosilylation of Ketones2007

    • Author(s)
      H. Ito, T. Kato, M. Sawamura
    • Journal Title

      Chem. Asian. J. 2

      Pages: 1436-1446

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Copper-catalyzed Enantioselective Substitution of Allylic Carbonates with Diboron: An Efficient Route to Optically Active (-Chiral Allylboronates2007

    • Author(s)
      H. Ito, S. Ito, Y. Sasaki, K. Matsuura, M. Sawamura
    • Journal Title

      J. Am. Chem. Soc. 129

      Pages: 14856-14857

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Enantioselective Addition of Terminal Alkynes to Aldehydes Catalyzed by a Cu (I)-TRAP Complex2007

    • Author(s)
      Y. Asano, K. Hara, H. Ito, M. Sawamura
    • Journal Title

      Org. Lett. 9

      Pages: 3901-3904

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Synthesis and Sructural Characterization of a Tetranuclear Platinum(II) Metallamacrocycle Containing 1,3-Diisocyanoarene Ligands2007

    • Author(s)
      H. Ito, T. Maeda, M. Sawamura
    • Journal Title

      Bull. Chem. Soc. Jpn 80

      Pages: 1981-1986

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Design and Synthesis of Isocyanide Ligands for Catalysis: Application to Rh-Catalyzed Hydrosilylation of Ketones2007

    • Author(s)
      H. Ito, T. Kato, M. Sawamura
    • Journal Title

      Chem. Asian. J 2

      Pages: 1436-1446

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Copper-catalyzed Enantioselective Substitution of Allylic Carbonates with Diboron: An Efficient Route to Optically Active a-Chiral Allylboronates2007

    • Author(s)
      H. Ito, S. Ito, Y. Sasaki, K. Matsuura, M. Sawamura
    • Journal Title

      J. Am. Chem. Soc 129

      Pages: 14856-14857

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Enantioselective Addition of Terminal Alkynes to Aldehydes Catalyzed by a Cu(l)-TRAP Complex2007

    • Author(s)
      Y. Asano, K. Hara, H. Ito, M. Sawamura
    • Journal Title

      Org. Lett. 9

      Pages: 3901-3904

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Copper-Catalyzed Enantioselective Substitution of Allylic Carbonates with Diboron: An Efficient Route to Optically Active α-Chiral Allylboronates2007

    • Author(s)
      Ito, H.; Ito, S.; Sasaki, Y.; Matsuura, K.; Sawamura, M.
    • Journal Title

      J. Am. Chem. Soc. 129

      Pages: 14856-14857

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Design and Synthesis of Isocyanide Ligands for Catalysis: Application to Rh-Catalyzed Hydrosilylation of Ketones2007

    • Author(s)
      Ito, H.; Kato, T.; Sawamura, M.
    • Journal Title

      Chem. Asian. J. 2

      Pages: 1436-1446

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Structural Characterization of a Tetranuclear Platinum(II)Metallamacrocycle Containing 1,3-Diisocyanoarene Ligands2007

    • Author(s)
      Ito, H.; Maeda, T.; Sawamura, M.
    • Journal Title

      Bull. Chem. Soc. Jpn. 80

      Pages: 1981-1986

    • NAID

      10019825166

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Addition of Terminal Alkynes to Aldehydes Catalyzed by a Cu(I)-TRAP Complex2007

    • Author(s)
      Asano, Y.; Hara, K.; Ito, H.; Sawamura, M.
    • Journal Title

      Org. Lett. 9

      Pages: 3901-3904

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of New Bulky Isocyanide Ligands and Their Use for Rh-catalyzed Hydrosilylation2006

    • Author(s)
      Hajime Ito
    • Journal Title

      Chem. Lett. 35巻9号

      Pages: 1038-1039

    • NAID

      10018063229

    • Related Report
      2006 Annual Research Report
  • [Presentation] 銅(I)-TRAP錯体触媒による末端アルキンのアルデヒドに対するエナンチオ選択的付加反応2008

    • Author(s)
      浅野 陽介, 伊藤 肇 澤村 正也
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Year and Date
      2008-03-27
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 不斉銅(I)触媒による光学活性アリルホウ素化合物の合成2008

    • Author(s)
      松浦 耕, 佐々木 悠祐, 伊藤 肇, 澤村 正也
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Year and Date
      2008-03-27
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 不斉銅(I)触媒による光学活性ボリルシリルシクロプロパン化合物の合成とその利用2008

    • Author(s)
      野々山 浩介, 佐々木 悠祐 伊藤 肇, 澤村 正也
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Year and Date
      2008-03-27
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 発光性メカノクロミズムを示す新規二核金(I)イソシアニド錯体2008

    • Author(s)
      齋藤 智久, 伊藤 肇, 喜多村 昇, 石坂 昌司, 加藤 昌子, 柘植 清志, 日夏 幸雄, 分島 亮, 澤村 正也
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Year and Date
      2008-03-27
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Enantioselective Addition Reaction of Terminal Alkynes to Aldehydes with Cu(I)-TRAP Catalyst2008

    • Author(s)
      Y. Asano, H. Ito, M. Sawamura
    • Organizer
      88th Spring Meeting Chemical Society of Japan
    • Place of Presentation
      Tokyo
    • Year and Date
      2008-03-27
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Copper-catalyzed Enantioselective Substitution of Allylic Carbonates with Diboron: A Route to Optically Active Allylboronates2008

    • Author(s)
      K. Matsuura, Y. Sasaki, H. Ito, M. Sawamura
    • Organizer
      88th Spring Meeting Chemical Society of Japan
    • Place of Presentation
      Tokyo
    • Year and Date
      2008-03-27
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] New Access to Optically Active Borylsilylcyclopropanes through Chiral Cu(I) Catalysi! T. Saito, H. Ito, N. Kitamura, S. Ishizaka, M. Kato, K. Tsuge, Y. Hinatsu2008

    • Author(s)
      K. Nonoyama, Y. Sasaki, H. Ito, M. Sawamura
    • Organizer
      88th Spring Meeting Chemical Society of Japan
    • Place of Presentation
      Tokyo
    • Year and Date
      2008-03-27
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Luminescence Mechanochromism of Novel Dinuclear Au(I)-Isocyanide Complex2008

    • Author(s)
      M. Wakeshima, M. Sawamura
    • Organizer
      88th Spring Meeting Chemical Society of Japan
    • Place of Presentation
      Tokyo
    • Year and Date
      2008-03-27
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 求核的なホウ素-銅(I)触媒活性種の発生:有機ホウ素化合物の革新的合成法2008

    • Author(s)
      伊藤 肇
    • Organizer
      京都大学グローバルCOEプログラム「物質科学の新基盤構築と次世代育成国際拠点」グローバルCOE有機若手ワークショップ
    • Place of Presentation
      京都府京都市
    • Related Report
      2007 Annual Research Report
  • [Presentation] 不斉銅(I)触媒による光学活性アリルホウ素化合物の合成2008

    • Author(s)
      松浦耕、佐々木悠祐、伊藤肇、澤村正也
    • Organizer
      日本化学会春季年会
    • Place of Presentation
      東京都豊島区
    • Related Report
      2007 Annual Research Report
  • [Presentation] 不斉銅(I)触媒による光学活性ボリルシリルシクロプロパン化合物の合成とその利用2008

    • Author(s)
      野々山浩介、佐々木悠祐、伊藤肇、澤村正也
    • Organizer
      日本化学会春季年会
    • Place of Presentation
      東京都豊島区
    • Related Report
      2007 Annual Research Report
  • [Presentation] 塩化金(I)ホスフィン錯体とヒドロシランから生成する金ヒドリドNMRと反応性2007

    • Author(s)
      齋藤 智久, 伊藤 肇, 澤村 正也
    • Organizer
      日本化学会第87春季年会
    • Place of Presentation
      吹田市
    • Year and Date
      2007-03-28
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Synthesis, Reactivities and NMR Studies of Gold(I) hydride Species Prepared from Gold(I)-phosphine Complex and Hydrosilanes2007

    • Author(s)
      T. Saito, H. Ito, M. Sawamura
    • Organizer
      87th Spring Meeting Chemical Society of Japan
    • Place of Presentation
      Suita
    • Year and Date
      2007-03-28
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Catalytic Generation of Nucleophilic Boron Species and Selective Synthesis of Allenylboron Compounds Using Copper Catalyst2007

    • Author(s)
      Y. Sasaki, H, Ito, M. Sawamura
    • Organizer
      87th Spting Meeting Chemical Society of Japan
    • Place of Presentation
      Suita
    • Year and Date
      2007-03-28
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 求核的ホウ素活性種の触媒的発生法と銅(I)触媒によるアレニルホウ素化合物の選択的合成2007

    • Author(s)
      佐々木 悠祐, 伊藤 肇, 澤村 正也
    • Organizer
      日本化学会第87春季年会
    • Place of Presentation
      吹田市
    • Year and Date
      2007-03-27
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 軸不斉イソシアニドの合成とロジウム触媒不斉ヒドロシリル化2007

    • Author(s)
      前田 剛志, 伊藤 肇, 澤村 正也
    • Organizer
      日本化学会第87春季年会
    • Place of Presentation
      吹田市
    • Year and Date
      2007-03-26
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Synthesis of Axially Chiral lsocyanide and Application to Rh-catalyezd Asymmetric Hydrosilylation2007

    • Author(s)
      T.Maeda, H. Ito, M. Sawamura
    • Organizer
      87th Spring Meeting Chemical Society of Japan
    • Place of Presentation
      Suita
    • Year and Date
      2007-03-26
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Synthesis of Optically Active 1-Silyl-2-borylcyclopropanes through Enantioselective Cu (I)-Catalysis with Diboron and Allylic Carbonates2007

    • Author(s)
      Hajime Ito
    • Organizer
      The 14th IUPAC International Symposium on Organometallic Chemistry Directed towards Organic Synthesis
    • Place of Presentation
      Nara
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Synthesis of Optically Active 1-Silyl-2-borylcyclopropanes through Enantioselective Cu(I)-Catalysis with Diboron and Allylic Carbonates2007

    • Author(s)
      H. Ito
    • Organizer
      The 14th IUPAC International symposium on Organometallic Chemistry Ditrcted towards Organic Synthesis
    • Place of Presentation
      Nara
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Enantioselective Cu(I)-Catalysis with Diboron and Allylic Carbonates: New Route to Optically Active Allylboronates and (2-Silylcyclopropyl)boronate2007

    • Author(s)
      H. Ito
    • Organizer
      4th Japanese-Sino Symposium on Organic Chemistry for Young Scientists
    • Place of Presentation
      千葉県成田市
    • Related Report
      2007 Annual Research Report
  • [Presentation] Synthesis and Luminescence of Au Complex of Tetrapod-shaped Isocyanide2007

    • Author(s)
      H. Ito
    • Organizer
      The 7th Tateshina Conference on Organic Chemistry
    • Place of Presentation
      長野県茅野市
    • Related Report
      2007 Annual Research Report
  • [Presentation] Synthesis of Optically Active 1-Silyl-2-borylcyclopropanes through Enantioselective Cu(I)-Catalysis with Diboron and Allylic Carbonates2007

    • Author(s)
      H. Ito
    • Organizer
      The 14th IUPAC International Symposium on Organometallic Chemistry Directed towards Organic Synthesis(OMCOS 14)
    • Place of Presentation
      奈良県奈良市
    • Related Report
      2007 Annual Research Report
  • [Presentation] 発光性金(I)-テトラポッド型イソシアニド錯体の合成2006

    • Author(s)
      伊藤 肇, 大島 直哉, 澤村 正也
    • Organizer
      第53回 有機金属化学討論会
    • Place of Presentation
      大阪
    • Year and Date
      2006-09-09
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Synthesis of Luminescent Tetrapod-shaped Gold(I) Isocyanide Complexes2006

    • Author(s)
      H. Ito, N. Oshima, M. Sawamura
    • Organizer
      53th Symposium of Organometallic Chemisty
    • Place of Presentation
      Osaka
    • Year and Date
      2006-09-09
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Patent(Industrial Property Rights)] 特許2007

    • Inventor(s)
      澤村正也, 伊藤肇
    • Industrial Property Rights Holder
      日本化学工業株式会社
    • Industrial Property Number
      2007-106170
    • Filing Date
      2007-04-19
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Patent(Industrial Property Rights)] 有機ホウ素化合物の製造法2007

    • Inventor(s)
      澤村正也, 伊藤肇
    • Industrial Property Rights Holder
      日本化学工業株式会社
    • Industrial Property Number
      2007-106170
    • Filing Date
      2007-04-19
    • Related Report
      2007 Annual Research Report

URL: 

Published: 2006-04-01   Modified: 2016-04-21  

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