Hydroxylamines as Oxygen Atom Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution

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Abstract

The viability of hydroxylamines as nucleophiles in transition-metal-catalyzed allylic substitutions was examined. We have found that the oxygen atom of hydroxylamines having an N-electron-withdrawing substituent (also known as hydroxamic acids) acts as a reactive nucleophile. The palladium-catalyzed O-allylic substitution of hydroxylamines with allylic carbonate afforded the linear hydroxylamines. The selective formation of the branched hydroxylamines was observed in iridium-catalyzed reaction. Regio- and enantioselective allylic substitution of the unsymmetrical phosphates with hydroxylamines was studied by using the iridium complex of chiral pybox ligand. The aqueous-medium reaction with hydroxylamines proceeded smoothly in the presence of Ba(OH)₂·H₂O to give the branched products with good enantioselectivities.

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This article has been cited by 10 ACS Journal articles (5 most recent appear below).

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  Enantioselective Iridium-Catalyzed Allylic Substitutions with Hydroxamic Acid Derivatives as N-Nucleophiles

  Martin Gärtner, Mascha Jäkel, Manuel Achatz, Christoph Sonnenschein, Olena Tverskoy, and Günter Helmchen
  Organic Letters2011 Article ASAP

  • Enantioselective Iridium-Catalyzed Allylic Substitutions with Hydroxamic Acid Derivatives as N-Nucleophiles

    Martin Gärtner, Mascha Jäkel, Manuel Achatz, Christoph Sonnenschein, Olena Tverskoy, and Günter Helmchen
    Organic Letters2011 Article ASAP

    Enantioselective Ir-catalyzed allylic aminations with hydroxamic acid derivatives are described. Catalysts were prepared in situ from [Ir(cod)Cl]2 or [Ir(dbcot)Cl]2, a phosphoramidite and base. In addition, pure (π-allyl)Ir complexes containing cod or ...

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• 

  Iridium-Catalyzed Enantioselective Allylic Substitution of O-Allyl Carbamothioates

  Qing-Long Xu, Wen-Bo Liu, Li-Xin Dai and Shu-Li You
  The Journal of Organic Chemistry2010 75 (13), 4615-4618

  • Iridium-Catalyzed Enantioselective Allylic Substitution of O-Allyl Carbamothioates

    Qing-Long Xu, Wen-Bo Liu, Li-Xin Dai and Shu-Li You
    The Journal of Organic Chemistry2010 75 (13), 4615-4618

    With an [Ir(COD)Cl]2/phosphoramidite ligand system, an allylic substitution of O-allyl carbamothioates was developed. The reaction proceeded in the favor of branched products with up to 93:7 branched-to-linear ratio, affording chiral S-allyl ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Enantioselective Synthesis of Allylic Esters via Asymmetric Allylic Substitution with Metal Carboxylates Using Planar-Chiral Cyclopentadienyl Ruthenium Catalysts

  Naoya Kanbayashi and Kiyotaka Onitsuka
  Journal of the American Chemical Society2010 132 (4), 1206-1207

  • Enantioselective Synthesis of Allylic Esters via Asymmetric Allylic Substitution with Metal Carboxylates Using Planar-Chiral Cyclopentadienyl Ruthenium Catalysts

    Naoya Kanbayashi and Kiyotaka Onitsuka
    Journal of the American Chemical Society2010 132 (4), 1206-1207

    An asymmetric allylic substitution with sodium carboxylate using a planar-chiral cyclopentadienyl ruthenium complex has been developed. Optically active allylic esters were prepared in good yields with high regio- and enantioselectivities.

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Iridium-Catalyzed, Regio- and Enantioselective Allylic Substitution with Aromatic and Aliphatic Sulfinates

  Mitsuhiro Ueda and John F. Hartwig
  Organic Letters2010 12 (1), 92-94

  • Iridium-Catalyzed, Regio- and Enantioselective Allylic Substitution with Aromatic and Aliphatic Sulfinates

    Mitsuhiro Ueda and John F. Hartwig
    Organic Letters2010 12 (1), 92-94

    The iridium-catalyzed allylation of sodium sulfinate to form branched allylic sulfones is reported. The reactions between various sodium sulfinates and achiral allylic carbonates occur in good yields, with high selectivity for the branched isomer, and ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Palladium- or Iridium-Catalyzed Allylic Substitution of Guanidines: Convenient and Direct Modification of Guanidines

  Hideto Miyabe, Kazumasa Yoshida, Valluru Krishna Reddy and Yoshiji Takemoto
  The Journal of Organic Chemistry2009 74 (1), 305-311

  • Palladium- or Iridium-Catalyzed Allylic Substitution of Guanidines: Convenient and Direct Modification of Guanidines

    Hideto Miyabe, Kazumasa Yoshida, Valluru Krishna Reddy and Yoshiji Takemoto
    The Journal of Organic Chemistry2009 74 (1), 305-311

    As a convenient and direct functionalization of guanidines, the transition metal-catalyzed allylic substitution of guanidines was studied. The guanidine derivatives bearing two electron-withdrawing substituents acted as reactive nucleophiles in the ...

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