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不斉ルイス酸触媒として機能する二核ロジウム(II)錯体の創製に関する研究

Research Project

Project/Area Number 16659001
Research Category

Grant-in-Aid for Exploratory Research

Allocation TypeSingle-year Grants
Research Field Chemical pharmacy
Research InstitutionHokkaido University

Principal Investigator

橋本 俊一  北海道大学, 大学院・薬学研究科, 教授 (80107391)

Co-Investigator(Kenkyū-buntansha) 穴田 仁洋  北海道大学, 大学院・薬学研究科, 助手 (90344473)
Project Period (FY) 2004 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 2005: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 2004: ¥1,700,000 (Direct Cost: ¥1,700,000)
Keywordsロジウム(II)錯体 / ルイス酸 / 不斉反応 / ヘテロDiels-Alder反応 / 向山アルドール反応 / カルボニル-エン反応 / 触媒
Research Abstract

当研究室で開発した不斉ロジウム(II)錯体のルイス酸触媒としての可能性に着目した反応開発研究を行い、以下の知見を得た。
1.酸素官能基一つで活性化された1,3-ジエンとアセチレニックアルデヒドとの不斉ヘテロDiels-Alder反応にRh_2(S-BPTPI)_4を用いると完壁なシス選択性と最高99%の不斉収率でテトラヒドロピラノン誘導体が得られることを見出し、本反応を鍵工程とする(-)-Centrolobineの触媒的不斉合成を行なった。また現在予備的知見ではあるが、Rh_2(S-BPTPI)_4は通常ルイス酸触媒を用いる不斉ヘテロDiels-Alder反応には用いられないRawalのジエンも適用可能(不斉収率97%)であることが分かった。母型錯体Rh_2(S-PTPI)_4の結晶構造とCoreyらによって提唱されている"ホルミルC-H…O水素結合"の概念に基づき本反応の立体反応経路の考察を行ない、基質アルデヒドのホルミル基の水素原子とアミダート配位子の酸素原子との間に生じる水素結合によるアルデヒドの配座固定が高いエナンチオ選択性発現に重要であることを明らかにした。
2.シリルケテンアセタールとアルデヒドの向山アルドール反応にRh_2(S-BPTPI)_4を用いると最高不斉収率94%でアルドール成績体が得られることを見出した。また、グリオキシル酸エステルとα-メチルスチレンの不斉カルボニル-エン反応では、Rh_2(S-PTPI)_4を用いた場合に50%eeと中程度の不斉誘起が観測された。

Report

(2 results)
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (12 results)

All 2005 2004

All Journal Article (12 results)

  • [Journal Article] Highly Enantio-and Diastereoselective Construction of 1,2-Disubstituted Cyclopentane Compounds by Dirhodium(II) Tetrakis[N-phthaloyl-(S)-terf-leucinate]-Catalyzed C-H Insertion Reactions of α-Diazoesters2005

    • Author(s)
      K.Minami et al.
    • Journal Title

      Adv.Synth.Catal. 347

      Pages: 1483-1487

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Practical Synthesis of Dirhodium(II) Tetrakis[N-phthaloyl-(S)-tert-leucinate]2005

    • Author(s)
      H.Tsutsui et al.
    • Journal Title

      Chem.Pharm.Bull. 53

      Pages: 1366-1368

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Dirhodium(II) Tetrakis[N-benzene-fused Phthaloyl-(S)-piperidinonate] as Chiral Lewis Acid : Catalytic Enantioselective Aldol Reactions of Acetate-derived Silylketene Acetals and Aldehydes2005

    • Author(s)
      T.Washio et al.
    • Journal Title

      Heterocycles 66

      Pages: 567-578

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Direct and Stereoselective Synthesis of 2-Acetamido-2-deoxy-β-D-glycopyranosides by Using the Phosphite Method2005

    • Author(s)
      R.Arihara et al.
    • Journal Title

      Angew.Chem., Int.Ed. 44

      Pages: 2245-2249

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Total synthesis of zaragozic acid C by an aldol-based strategy2005

    • Author(s)
      S.Nakamura et al.
    • Journal Title

      Tetrahedron 61

      Pages: 11078-11106

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Chiral Phosphine Oxide BINAPO as a Catalyst for Enantioselective Allylation of Aldehydes with Allyltrichlorosilanes2005

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

      Tetrahedron Lett. 46

      Pages: 157-159

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Chiral Phosphine Oxide BINAPO as a Catalyst for Enantioselective Allylation of Aldehydes with Allyltrichlorosilanes2005

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

      Tetrahedron Letters 46

      Pages: 157-159

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Direct and Stereoselective Synthesis of 2-Acetamido-2-deoxy-β-D-glycopyranosides by Using the Phosphite Method2005

    • Author(s)
      R.Arihara et al.
    • Journal Title

      Angew.Chem.Int.Ed. 44(発表予定)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Enantioselective Aldol Reactions of Trichlorosilyl Enol Ethers Catalyzed by Chiral N,N'-Dioxides and Monodentate N-Oxides2004

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

      Tetrahedron Letters 45

      Pages: 61-64

    • Related Report
      2004 Annual Research Report
  • [Journal Article] A New Dirhodium(II) Carboxamidate Complex as a Chiral Lewis Acid Catalyst for Enantioselective Hetero-Diels-Alder Reactions2004

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

      Angew.Chem.Int.Ed. 43

      Pages: 2665-2668

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Enantioselective Aldol Reaction of Trimethoxysilyl Enol Ether Catalyzed by Lithium Binaphtholate2004

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

      Organic Letters 6

      Pages: 3763-3765

    • Related Report
      2004 Annual Research Report
  • [Journal Article] A highly stereoselective construction of 1,2-trans-β-glycosidic linkages capitalizing on 2-azido-2-deoxy-D-glycosyl diphenyl phosphates as glycosyl donors2004

    • Author(s)
      T.Tsuda et al.
    • Journal Title

      Tetrahedron 60

      Pages: 10711-10737

    • Related Report
      2004 Annual Research Report

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Published: 2004-04-01   Modified: 2016-04-21  

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