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2005 Fiscal Year Final Research Report Summary

Bond Formation in Tight Coordination Sphere on Small Transition metal

Research Project

Project/Area Number 16550096
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

OGOSHI Sensuke  Osaka University, Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (30252589)

Project Period (FY) 2004 – 2005
Keywordsnickel / oxidative cyclization / carbonyl / alkene / butadiene / organoaluminum
Research Abstract

The addition of 1,5-hexenal or o-allylbenzaldehyde to a solution of Ni(cod)_2 and PR_3 (PCy_3 or PPh_3,1 equiv) gave η^2-alkene:η^2-aldehyde complexes quantitatively. Heating the solution at 60℃ or 80℃ resulted in the oxidative cyclization to give nickelacycle complexes. The direct observation of oxidative cyclization from η^2-carbonyl:η^2-olefin coordination complex to five membered metalacycle has not been reported even with early transition metal systems. AlMe_3 promoted the oxidative cyclization of η^2:η^2-2-allylacetophenone- or η^2:η^2-2-allylbenzophenone nickel complex to give an intriguing nickel-aluminum dinuclear complex. The molecular structure was determined by X-ray diffraction analysis. This complex is a nice model as an intermediate in the transmetallation process. Moreover, the cycloisomerization can proceed catalytically in THF.
The reversible oxidative cyclization of dienes and aldehydes with nickel(0) proceeded to give η^3:η^1-allylalkoxynickel complexes. The treatmen … More t of these complexes with carbon monoxide led to the formation of the corresponding lactone and/or the regeneration of a butadiene and an aldehyde concomitant with the formation of Ni(CO)_3(PCy_3). The scission of nickel-oxygen bond of the allylalkoxy complexes with ZnMe_2 leading to η^3-allyl(methyl)nickel was very efficient to suppress the reverse reaction of the oxidative cyclization. The methylated η^3-allylnickel compound underwent the reductive elimination. The carbonylative coupling reaction of the η^3-allyl(methyl)nickel proceeded as well under a carbon monoxide atmosphere. Similarly, the addition of Me_3SiCl to η^3:η^1-allylalkoxynickel complexes was also efficient for the inhibition of the reverse reaction. The resulting η^3-1-siloxyethylallylnickel complex was treated with carbon monoxides followed by the addition of MeOH to give the expected hydroxyester. This method is efficient as well even for the η^3:η^1-allyl(alkoxy)nickel complex containing acetone as a component, which was so prone to undergo the reverse reaction hampering its isolation. The isolation of η^3:η^1-qllylalkoxynickel complex containing ketone as a component was made easier by the use of heavier butadiene and ketone, such as 2,3-dibenzyl-1,3-butadine and benzophenone or by the use of cyclobutanone. The reaction with styrene oxide gave the η^3:η^1-allylalkoxynickel containing phenylacetoaldehyde, an isomer of styrene oxide. Less

  • Research Products

    (10 results)

All 2006 2005 2004 Other

All Journal Article (10 results)

  • [Journal Article] Formation of Nickeladihydropyran by Oxidative Addition of Cyclopropyl Ketone. Key Intermediate in Nickel-Catalyzed Cycloaddition2006

    • Author(s)
      Sensuke Ogoshi
    • Journal Title

      Journal of the American Chemical Society 128・16

      Pages: 5350-5351

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Reversible Carbon-Carbon Bond Formation between 1,3-Dienes and Alde Hyde or Ketone on Nickel(0)2006

    • Author(s)
      Sensuke Ogoshi
    • Journal Title

      Journal of the American Chemical Society 128(in press)

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Formation of Nickeladihydropyran by Oxidative Addition of Cyclopropyl Ketone. Key Intermediate in Nickel-Catalyzed Cycloaddition2006

    • Author(s)
      Sensuke Ogoshi
    • Journal Title

      Journal of the American Chemical Society 128,(16)

      Pages: 5350-5351

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] AlMe_3-Promoted Oxidative Cyclization of η^2-Alkene and η^2-Ketone on Nickel(0). Observation of Intermediate in Methyl Transfer Process2005

    • Author(s)
      Sensuke Ogoshi
    • Journal Title

      Journal of the American Chemical Society 127・37

      Pages: 12810-12811

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] AlMe_3-Promoted Oxidative Cyclization of η^2-Alkene and η^2-Ketone on Nickel(0). Observation of Intermediate in Methyl Transfer Process2005

    • Author(s)
      Sensuke Ogoshi
    • Journal Title

      Journal ofthe American Chemical Society 127,(37)

      Pages: 12810-12811

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Direct Observation of Oxidative Cyclization of η^2-Alkene and η^2-Alddehyde on Ni(0) Center.Significant Acceleration by Addition of Me_3SiOTf2004

    • Author(s)
      Sensuke Ogoshi
    • Journal Title

      Journal of the American Chemical Society 126・38

      Pages: 11802-11803

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Dimerization of terminal alkynes catalyzed by a nickel complex having a bulky phosphine ligand2004

    • Author(s)
      Sensuke Ogoshi
    • Journal Title

      Chemical Communication 23

      Pages: 2732-2733

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Direct Observation of Oxidative Cyclization of η^2-Alkene and η^2-Alddehyde on Ni(0) Center. Significant Acceleration by Addition of Me_3SiOTf2004

    • Author(s)
      Sensuke Ogoshi
    • Journal Title

      Journal of the American Chemical Society 126,(38)

      Pages: 11802-11803

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Dimerization of terminal alkynes catalyzed by a nickel complex having a bulky phosphine ligand2004

    • Author(s)
      Sensuke Ogoshi
    • Journal Title

      Chemical Communications 23

      Pages: 2732-2733

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Reversible Carbon-Carbon Bond Formation between 1,3-Dienes and Aldehyde or Ketone on Nickel(0)

    • Author(s)
      Sensuke Ogoshi
    • Journal Title

      Journal of the American Chemical Society (in press)

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

URL: 

Published: 2007-12-13  

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