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2002 Fiscal Year Final Research Report Summary

Development of Novel Synthetic Reactions Utilizing Transition-Metal Complexes Containing Carbon-Metal Multiple Bonds

Research Project

Project/Area Number 12440176
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionTokyo Institute of Technology

Principal Investigator

IWASAWA Nobuharu  Tokyo Institute of Technology, Department of Chemistry, Professor, 大学院・理工学研究科, 教授 (40168563)

Project Period (FY) 2000 – 2002
Keywordsvinylidene complex / carbene complex / one-electron reduction / benzopyranylidene complex / metal-containing carbonyl ylide / polycyclic indole / tungstencarbonyl complex
Research Abstract

This research has focused on the development of novel carbon-carbon bond forming reactions utilizing the transition metal complexes containing carbon-metal multiple bonds.
1) Two types of novel reactive species were generated by one-electron reduction of Fischer-type carbene complexes. In the case of tungsten complexes, one-electron reduction generated anion radical species, which added to electron-deficient olefins to give addition products. In the case of chromium complexes, carbonyl insertion occurred to give acyl chromate complexes, which underwent 1, 4-addition to various electron-deficient olefins.
2) Treatment of o-ethynylphenylketone derivatives with W(CO_5・THF gave novel benzopyranylidene complexes through electrocyclization of vinylidene intermediates. These complexes readily underwent inverse electron demand Diels-Alder reaction with electron-rich olefins to give naphthalene derivatives in good yield. Furthermore, we have developed a novel method for the generation of metal-containing carbonyl ylides by the reaction of o-ethynylphenyl ketones with W(CO)_5・THF. The [3+2]-cycloaddition of these ylides with electron-rich alkenes followed by insertion of the resulting tungsten carbene moiety into a neighboring C-H bond realizes the construction of complex cyclic carbon frameworks in a single step. This reaction was further developed into a novel method for the synthesis of polycyclic indole derivatives through the generation of metal-containing azomethine ylides.
3) Treatment of ω-acetylenic silyl enol ethers with a catalytic amount of W(CO)_5・L realizes an effective electrophilic activation of the acetylenic moiety for the attack of the silyl enol ether part to give cyclized products in high yield. This reaction has been studied extensively and a variety of synthetically useful reactions have been developed.

  • Research Products

    (26 results)

All Other

All Publications (26 results)

  • [Publications] K.Fuchibe: "A Novel Use of the Anions of Fischer-type Carbene Complexes as Alkenyl Metallic Species"Tetrahedron. 56. 4907-4915 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Iwasawa: "Novel Synthesis of Pentacarbonylbenzopyranylidenetungsten(0) Complexes and their Diels-Alder Reaction with Electron-Rich Alkenes"J.Am.Chem.Soc.. 122. 10226-10227 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Fuchibe: "Reactions of Novel Reactive Species Generated by Samarium(II)-Mediated One-Electron Reduction of Fischer-Type Carbene Complexes"Org.Lett.. 2. 3297-3299 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Iwasawa: "Reactions of silyl-substituted Fischer-type carbene complexes with silanes"J.Organomet.Chem.. 617-618. 741-743 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Iwasawa: "Generation and Reaction of Metal-Containing Carbonyl Ylides : Tandem [3+2]-Cycloaddition-Carbene Insertion Leading to Novel Polycyclic Compounds"J.Am.Chem.Soc.. 123. 5814-5815 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Iwasawa: "A Novel Reaction for Annulation onto α,β-Unsaturated Ketones : W(CO)_5・L Promoted Exo-and Endo-Selective"Org.Lett.. 3. 3871-3873 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Miura: "Reactions of Iodinated Vinylidene Complexes Generated from 1-Iodo-1-alkynes and W(CO)_5(thf)"J.Am.Chem.Soc.. 124. 518-519 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Kusama: "Tandem Cyclizations of Benzopyranylidenetungsten(0) Complexes with Electron-Rich Dienes for the Stereoselective Synthesis of Polycyclic Carbon Skeletons"Chem.Lett.. 124-125 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Kusama: "W(CO)_5-Amine Catalyzed Exo-and Endo-Selective Cyclizations of ω-Alkynyl Silyl Enol Ethers: A Highly Useful Method for the Construction of Polycyclic Compounds"Org.Lett.. 4. 2569-2571 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Kusama: "A Facile Method for the Synthesis of Polycyclic Indole Derivatives : The Generation and Reaction of Tungsten-Containing Azomethine Ylides"J.Am.Chem.Soc.. 124. 11592-11593 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N.Iwasawa: "An Efficient Method for Cyclopentene Annulation onto α,β-Unsaturated Ketones : W(CO)_5(L)-Catalyzed 5-Endo-Dig Cyclization of 6-Siloxy-5-en-1-ynes"Org.Lett.. 4. 4463-4466 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Fuchibe: "Generation of Reactive Species by One-Electron Reduction of Fischer-Type Carbene Complexes of Group 6 Metals and Their Use for Carbon-Carbon Bond Formation"Chem.Eur.J.. 9. 905-914 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Miura: "W(CO)_5(L)-Catalyzed Endo-Selective Cyclization of Allenyl Silyl Enol Ethers : An Efficient Method for the Cyclopentene Annulation onto α,β-Unsaturated Ketones"Org.Lett.. 5. 1725-1728 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Fuchibe: "A Novel Use of the Anions of Fischer-type Carbene Complexes as Alkenyl Metallic Species"Tetrahedron. 56. 4907-4915 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Iwasawa: "Novel Synthesis of Pentacarbonylbenzopyranylidenetungsten(0) Complexes and their Diels-Alder Reaction with Electron-Rich Alkenes"J. Am. Chem. Soc.. 122. 10226-10227 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Fuchibe: "Reactions of Novel Reactive Species Generated by Samarium(II)-mediated One-electron Reduction of Fischer-type Carbene Complexes"Org. Lett.. 2. 3297-3299 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Iwasawa: "Reactions of Silyl-substituted Fischer-type Carbene Complexes with Silanes"J. Organomet. Chem.. 617-618. 741-743 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Iwasawa: "Generation and Reaction of Metal-Containing Carbonyl Ylides : Tandem [3+2]-Cycloaddition-Carbene Insertion Leading to Novel Polycyclic Compounds"J. Am. Chem. Soc.. 123. 5814-5815 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Iwasawa: "A Novel Reaction for Annulation onto α, β-Unsaturated Ketones : W(CO)_5=L Promoted Exo and Endo Selective Cyclizations of ω-Acetylenic Silyl Enol Ethers Prepared by 1, 4-Addition of Propargyl Malonate to Enones"Org. Lett.. 3. 3871-3873 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Miura: "Reactions of lodinated Vinylidene Complexes Generated from 1-Iodo-l-alkynes and W(CO)_5・THF"J. Am. Chem. Soc.. 124. 518-519 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Kusama: "Tandem Cyclizations of Benzopyranylidenetungsten(0) Complexes with Electron-Rich Dienes for the Stereoselective Synthesis of Polycyclic Carbon Skeletons"Chem. Lett.. 124-125 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Kusama: "W(CO)_5-Amine Catalyzed Exo- and Endo-Selective Cyclizations of ω-Alkynyl Silyl Enol Ethers : A Highly Useful Method for the Construction of Polycyclic Compounds"Org. Lett.. 4. 2569-2571 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Kusama: "A Facile Method for the Synthesis of Polycyclic Indole Derivatives : The Generation and Reaction of Tungsten-Containing Azomethine Ylides"J. Am. Chem. Soc.. 124. 11592-11593 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] N. Iwasawa: "An Efficient Method for the Cyclopentene Annulation onto α, β(3-Unsaturated Ketones : W(CO)_5(L) Catalyzed 5-Endo-Dig Cyclization of 6-Siloxy-5-en-1-ynes"Org. Lett.. 4. 4463-4466 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Fuchibe: "Generation of Reactive Species by One-Electron Reduction of Fischer-Type Carbene Complexes of Group 6 Metals and Their Use for Carbon-Carbon Bond Formations"Chem. Eur. J.. 9. 905-914 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Miura: "W(CO)_5(L)-Catalyzed Endo-Selective Cyclization of Allenyl Silyl Enol Ethers : An Efficient Method for the Cyclopentene Annulation onto α, β-Unsaturated Ketones"Org. Lett.. 5. 1725-1728 (2003)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2004-04-14  

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