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カルベン配位子の特性を利用した新規反応の開発と不斉合成への応用

Research Project

Project/Area Number 14703031
Research Category

Grant-in-Aid for Young Scientists (A)

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

Principal Investigator

佐藤 美洋  北海道大学, 大学院・薬学研究科, 教授 (90226019)

Project Period (FY) 2002 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥28,990,000 (Direct Cost: ¥22,300,000、Indirect Cost: ¥6,690,000)
Fiscal Year 2004: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2003: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2002: ¥21,190,000 (Direct Cost: ¥16,300,000、Indirect Cost: ¥4,890,000)
Keywords含窒素ヘテロ環カルベン / N-heterocyclic carbene / 1,3-ジエン / アルデヒド / ニッケル / 不斉合成 / 求核性カルベン / 辻-トロスト反応 / アリルシラン / イミダゾリニウム / イミダゾリウム / パラジウム / π-アリルパラジウム / ビスメタル化 / シリルスタナン / 環化反応 / カルベン
Research Abstract

我々はこれまで含窒素ヘテロ環カルベン(NHC)の配位子としての機能に興味を持ち研究を展開し,NHCが様々な反応においてホスフィン配位子とは異なる反応性や立体選択性を示すことを見い出してきた.その中の一つに,ニッケル触媒によって進行する1,3-ジエンとアルデヒドとの分子間カップリング反応が挙げられる.この反応ではトリアルキルシラン存在下,配位子としてPPh_3を用いると立体選択的E-オレフィンをもつカップリング体が生成するが,NHC配位子を用いると反応はZ-選択的に進行し,Z-オレフィンをもつカップリング体が生成する.ところで光学活性NHC配位子を用いた「触媒的不斉合成」に関する研究例は極めて少なく,大変興味が持たれる.そこで本研究課題では,光学活性NHC配位子を用いた上記の反応の不斉反応への展開を検討した.Et_3SiH存在下,20mol%のNi(cod)_2に対し,配位子として1,3-bis[(1S)-phenylethyl]imidazoyl-2-ylideneを用い反応を行ったところ,反応はZ-選択的に進行した.また,この時カップリング体の鏡像異性体過剰率は28%eeを示した.一方,このNHC配位子と共通の不斉環境を有していると考えられる還元型の1,3-bis[(1S)-phenylethyl]-4,5-dihydroimidazoyl-2-ylideneを用い反応を行ったところ,Z-選択性は大きく低下した.これらの反応の錯体調製時には,imidazolium塩またはimidazolinium塩を前駆体として用い,対応するカルベンを調製している.従って,還元型NHCの場合はimidazolinium塩の酸性度が低いため,系内で十分にカルベンが発生せずZ-選択性の低下を招いたと考えられた.そこで錯体調製条件を種々検討したところ,imidazolinium塩から調製した還元型NHCにおいてもZ-選択的なカップリング反応を実現することが出来た.今後更に,新たな光学活性NHCの創製により鏡像異性体過剰率の向上を目指すと共に,他の反応への応用を展開したい.

Report

(3 results)
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (29 results)

All 2005 2004 Other

All Journal Article (11 results) Publications (18 results)

  • [Journal Article] Synthesis of Isoquinoline Derivatives Using ROM-RCM of Cyclobutene-Yne.2005

    • Author(s)
      Miwako Mori
    • Journal Title

      The Journal of Organic Chemistry 70巻・3号

      Pages: 1066-1069

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Nickel-Catalyzed Regioselective Synthesis of Tetrasubstituted Alkene Using Alkylative Carboxylation of Disubstituted Alkyne.2005

    • Author(s)
      Kazuya Shimizu
    • Journal Title

      Organic Letters 7巻・2号

      Pages: 195-197

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Ligand-Controlled Highly Stereoselective Syntheses of E- and Z-Allylsilanes from Diene and Aldehydes Using Nickel Complex.2004

    • Author(s)
      Rieko Sawaki
    • Journal Title

      Organic Letters 6巻・7号

      Pages: 1131-1133

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Palladium-Catalyzed Asymmetric Allylic Substitution of 2-Arylcyclohexenol Derivative : Asymmetric Total Syntheses of (+)-Crinamine, (-)-Haemanthidine, and (+)-Pretazettine.2004

    • Author(s)
      Toyoki Nishimata
    • Journal Title

      The Journal of Organic Chemistry 69巻・6号

      Pages: 1837-1843

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Arylnaphthalene Lignans through Pd-Catalyzed [2+2+2] Cocyclization of Arynes and Diynes : Total Synthesis of Taiwanins C and E.2004

    • Author(s)
      Yoshihiro Sato
    • Journal Title

      Angewandte Chemie international edition 43巻・18号

      Pages: 2436-2440

    • Related Report
      2004 Annual Research Report
  • [Journal Article] ROM-RCM of Cycloalkene-Yne.2004

    • Author(s)
      Tsuyoshi Kitamura
    • Journal Title

      Tetrahedron 60巻・34号

      Pages: 7375-7389

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Zirconium-Mediated Intramolecular Cyclization of Yne-Imine.2004

    • Author(s)
      Muneyoshi Makabe
    • Journal Title

      Synthesis 9号

      Pages: 1369-1374

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Nitrogen Fixation : Synthesis of Heterocycles Using Molecular Nitrogen as a Nitrogen Source.2004

    • Author(s)
      Miwako Mori
    • Journal Title

      Bulletin of the Chemical Society of Japan 77巻・9号

      Pages: 1655-1670

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Intramolecular Cyclization of Ene-Imine Using Dibutylzirconocene.2004

    • Author(s)
      Muneyoshi Makabe
    • Journal Title

      The Journal of Organic Chemistry 69巻・19号

      Pages: 6238-6243

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Synthetic Study of (+)-Anthramycin.2004

    • Author(s)
      Tsuyoshi Kitamura
    • Journal Title

      Tetrahedron 60巻・43号

      Pages: 9649-9657

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Synthesis of Bicyclic Compounds From Propargyl Esters Using Palladium Catalyst Bearing Bidentate Ligand.2004

    • Author(s)
      Masaya Tsubakiyama
    • Journal Title

      Heterocycles 64巻・1号

      Pages: 27-31

    • Related Report
      2004 Annual Research Report
  • [Publications] Yoshihiro Sato: "Novel Rh(I)-Catalyzed Cycloisomerization of 1,3-Diene with Alkene in a Tether : A Competitive Reaction with a [4+2] Cycloaddition"Organometallics. 22巻・1号. 30-32 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshihiro Sato: "Pd-Catalyzed Allylic Substitution Using Nucleophilic N-Heterocyclic Carbene as a Ligand"Org.Lett.. 5巻・1号. 31-33 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshihiro Sato: "Pd(0)-Catalyzed Bismetallative Cyclization of Enynes in the Presence of Bu_3SnSiMe_3 Using N-Heterocyclic Carbene as a Ligand"Adv.Synth.Catal.. 345巻・4号. 488-491 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Miwako Mori: "Zirconium-Catalyzed Enantiotopic Group-Selective Synthesis of Hydrindanes"Tetrahedron Lett.. 44巻. 3797-3800 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Miwako Mori: "Novel Alkenylative Cyclization Using a Ruthenium Catalyst"J.Am.Chem.Soc.. 125巻・19号. 5606-5607 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Miwako Mori: "A Novel and General Synthetic Pathway to Strychnos Indole Alkaloids"J.Am.Chem.Soc.. 125巻・32号. 9801-9807 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshihiro Sato: "Further Studies on Palladium-Catalyzed Bismetallative Cyclization of Enynes in the Presence of Bu_3SnSiMe_3"J.Organomet.Chem.. 687巻. 392-402 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshihiro Sato: "Further Studies on Ni(0)-Caralyzed Cyclization of a Branched 1,3-Diene and Tethered Aldehyde via Oxanickelacycle Intermediate"J.Organomet.Chem.. 688巻. 36-48 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshihiro Sato: "Novel Synthesis of Conjugated Dienes Attached to a Quaternary Carbon Center via Pd(0)-Catalyzed Deconjugative Allylation of Alkenylidenemalonates"J.Org.Chem.. 68巻・25号. 9858-9860 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Toyoki Nishimata: "Palladium-Catalyzed Asymmetric Allylic Substitution of 2-Arylcyclohexenol Derivative"J.Org.Chem.. (印刷中). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Rieko Sawaki: "Ligand-Controlled Highly Stereoselective Syntheses of E- and Z-Allylsilanes from Diene and Aldehydes Using Nickel Complex"Org.Lett.. (印刷中). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshihiro Sato: "Novel Synthesis of Arylnaphthalene Lignans via Pd-Catalyzed [2+2+2] Cocyclization of Aryne and Diyne : Total Syntheses of Taiwanins C and E."Angew.Chem.Int.Ed.. (印刷中). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshihiro Sato: "Ni(0)-Catalyzed Bismetallative Cyclization of 1,3-Diene and a Tethered Aldehyde in the Presence of Bu_3SnSiMe_3"Chem. Lett.. 1号. 18-19 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Yoshihiro Sato: "Nickel-Catalyzed Intermolecular Coupling of 1,3-Dienes and Aldehydes via Transmetalation of Nickelacycles with Diisobutylaluminum Acetylacetonate"J. Org. Chem.. 67巻3号. 656-662 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Yoshihiro Sato: "A New Method for the Synthesis of Cycloheptenones via a Rh(1)-Catalyzed Intramolecular Hydroacylation of 4,6-Dienals"Angew. Chem. Int. Ed.. 41巻7号. 1218-1221 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Tsuyoshi Kitamura: "Effects of Substituents on the Multiple Bonds on Ring-Closing Metathesis of Enynes"Adv. Synth. Catal. 344巻. 678-693 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Miwako Mori: "Ruthenium-Catalyzed ROM-RCM of Cycloalkene-Yne"Org. Lett.. 4巻. 3855-3858 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Yoshihiro Sato: "Asymmetric Cyclization of ω-Formyl-1,3-dienes Catalyzed by a Zerovalent Nickel Complex in the Presence of Silanes"J. Org. Chem.. 67巻26号. 9310-9317 (2002)

    • Related Report
      2002 Annual Research Report

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

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