Efficient Access to Conjugated Dienones and Diene-diones from Propargylic Alcohols and Enolizable Ketones: A Tandem Isomerization/Condensation Process Catalyzed by the Sixteen-Electron Allyl-Ruthenium(II) Complex [Ru(η3-2-C3H4Me)(CO)(dppf)] [SbF6]

Authors

  • Victorio Cadierno,

    1. Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica “Enrique Moles” (Unidad Asociada al CSIC), Facultad de Química, Universidad de Oviedo, 33071 Oviedo, Spain Fax: +(34)-985-103446
    Search for more papers by this author
  • Josefina Díez,

    1. Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica “Enrique Moles” (Unidad Asociada al CSIC), Facultad de Química, Universidad de Oviedo, 33071 Oviedo, Spain Fax: +(34)-985-103446
    Search for more papers by this author
  • Sergio E. García-Garrido,

    1. Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica “Enrique Moles” (Unidad Asociada al CSIC), Facultad de Química, Universidad de Oviedo, 33071 Oviedo, Spain Fax: +(34)-985-103446
    Search for more papers by this author
  • José Gimeno,

    1. Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica “Enrique Moles” (Unidad Asociada al CSIC), Facultad de Química, Universidad de Oviedo, 33071 Oviedo, Spain Fax: +(34)-985-103446
    Search for more papers by this author
  • Noel Nebra

    1. Departamento de Química Orgánica e Inorgánica, Instituto Universitario de Química Organometálica “Enrique Moles” (Unidad Asociada al CSIC), Facultad de Química, Universidad de Oviedo, 33071 Oviedo, Spain Fax: +(34)-985-103446
    Search for more papers by this author

Abstract

A large variety of conjugated dienones R1R2C[DOUBLE BOND]CHCH[DOUBLE BOND]C(R3)C([DOUBLE BOND]O)R4 and diene-diones R1R2C[DOUBLE BOND]CHCH[DOUBLE BOND]C{C([DOUBLE BOND]O)R3}C([DOUBLE BOND]O)R4 have been synthesized in high yields by reacting terminal propargylic alcohols HC[TRIPLE BOND]CCR1R2(OH) with enolizable ketones R3CH2C([DOUBLE BOND]O)R4 and β-dicarbonyl compounds R3C([DOUBLE BOND]O)CH2C([DOUBLE BOND]O)R4, respectively. The process, which is catalyzed by the 16e-3-allyl)-ruthenium(II) complex [Ru(η3-2-C3H4Me)(CO)(dppf)] [SbF6] associated with CF3CO2H, involves the initial isomerization of the propargylic alcohol into the corresponding α,β-unsaturated aldehyde R1R2C[DOUBLE BOND]CHCHO (Meyer–Schuster rearrangement) and subsequent aldol-type condensation.

Ancillary