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1991 Fiscal Year Final Research Report Summary

Development of Organic Synthetic Reaction Utilizing Charge Reversal of pi-Allylpalladium Complex

Research Project

Project/Area Number 02640407
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionSophia University

Principal Investigator

MASUYAMA Yoshiro  Sophia University, Faculty of Sci. and Tech., Assistant, 理工学部, 助手 (30138375)

Project Period (FY) 1990 – 1991
KeywordsCarbonyl Allylation / Charge Reversal / pi-Allylpalladium / Stannous Chloride / Allylic Alcohol / Vinyl Epoxide / Diastereoselection / Chelation
Research Abstract

I have found that palladium-catalyzed carbonyl allylation by allylic alcohols with SnCl_2 smoothly proceeds in aqueous medium under air. Allylic alcohols, preparing pi-allylpalladium complexes, function as synthons of allylic carbanions. In other words, this implies the apparent charge reversal of electrophilic pi-allylpalladium complexes. The carbonyl allylation by allylic alcohols can achieve high chemo-, regio-, and diastereoselection by the choice of solvent. Here I report about the full scope, limitations, and mechanism of this new process : 1. ^1H, ^<13>C, and ^<119>Sn NMR investigation has elucidated that the actual allylating agent in the carbonyl allylation by allyl alcohol in dry medium is allyltrichlorotin, which is prepared via (1) oxidative addition of allyl alcohol to Pd (O) complex with SnCl_2, (2) insertion of SnCl_2 to pi-allylpalladium complex, followed by (3) reductive elimination of pi-allylpalladium trichlorostannate. 2. This carbonyl allylation in polar solvent has been applied to chelation-controlled diastereoselection ; (1) the chelation of omega-hydroxy carbonyl compound to Sn (IV) in allylic tin, (2) the chelation of intramolecular ethoxycarbonyl group to Sn (IV) in 1-substituted 2-ethoxycarbonyl-2-propenyltin, and (3) the chelation of intramolecular hydroxy group to Sn (IV) in 4-substituted 4-hydroxy-2-butenyltin. 3. Intramolecular carbonyl allylation has been carried out using (1) 4-hydroxymethyl-4-pentenals prepared by Claisen rearrangement of 2-hydroxymethylallyl vinyl ethers and (2) 7-hydroxy-5-heptenals prepared by oxy-Cope rearrangement of 3-hydroxy-4-hydroxymethyl-1, 5-hexadienes. 4. Ultrasound-promoted carbonyl allylation by 3-substituted allylic alcohol in nonpolar solvent has caused inversed regiocontrol to the carbonyl allylation in polar solvent.

  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] Yashiro Masuyama: "Paladium-Catalyzed Carbonyl Allylation by 2-(Hydroxymethyl)acrylate Derivatives:Synthesis of α-Methylene-γ-butyrolactones" Tetrahedron Lett.32. 225-228 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Jun P.Takahara: "Diastereoselective Allylation of ω-Hydroxy Carbonyl Compounds by Allylic Alcohols with Pd-SnCl_2" Chem.Lett.879-882 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshiro Masuyama: "Carbonyl Allylation by Vinyl Epoxides with SnCl_2-TBA or SnCl_2-LiI;Application to Diastereoselective Synthesis of 1,3-Diols" J.Chem.Soc.,Perkin Trans.1. 2598-2599 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Jun P.Takahara: "Paladium-Catalyzed Carbonyl Allylation by Allylic Alcohols with CnCl_2" J.Am.Chem.Soc.114. (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 増山 芳郎: "πーアリルパラジウム錯体の見かけ上の電荷反転:アリルアルコ-ル類によるカルポニルーアリル化反応への応用" 有機合成化学協会誌. 50. 202-212 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshiro Masuyama: ""Advances in Metal-Organic Chemistry",ed by L.S.Liebeskind,Vol.3" JAI Press Inc., (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y. Masuyama, Y. Nimura, and Y. Kurusu: "Palladium-Catalyzed Carbonyl Allylation by 2-(Hydroxymethyl) Acrylate Derivatives : Synthesis of alpha-Methylene-gamma-butyrolactones" Tetrahedron Lett.32. 225-228 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] J. P. Takahara, Y. Masuyama, and Y. Kurusu: "Diastereoselective Allylation of omega-Hydroxy Carbonyl Compounds by Allylic Alcohols with Pd-SnCl_2" Chem. Lett.879-882 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Masuyama, J. Nakata, and Y. Kurusu: "Carbonyl Allylation by Vinyl Epoxides with SnCl_2-TBA or SnCl_2-LiI ; Application to Diastereoselective Synthesis of 1, 3-Diols" J. Chem. Soc., Perkin Trans. 1. 2598-2599 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Masuyama: "Apparent Charge Reversal of pi-Allylpalladium Complex : Application to Carbonyl Allylation by Allylic Alcohols" J. Synth. Org. Chem., Jpn.50. 202-212 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] J. P. Takahara, Y. Masuyama, and Y. Kurusu: "Palladium-Catalyzed Carbonyl Allylation by Allylic Alcohols with SnCl_2" J. Am. Chem. Soc.114.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Masuyama: "Advances in Metal-Organic Chemistry, " ed by L. S. Liebeskind Vol. 3. Palladium-Catalyzed Carbonyl Allylation via pi-Allylpalladium Complex, (1992)

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

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Published: 1993-03-16  

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