Transition metal-catalysed [2+2+2] cycloaddition reactions. Methodology and mechanism

• Autores: Magda Parera Briansó
• Directores de la Tesis: Anna Roglans i Ribas (dir. tes.), Anna Pla Quintana (dir. tes.)
• Lectura: En la Universitat de Girona ( España ) en 2014
• Idioma: inglés
• Tribunal Calificador de la Tesis: Yolanda Díaz Giménez (presid.), Rosa M. Sebastián Pérez (secret.), Marko Hapke (voc.)
• Materias:
  • Física
    • Física del estado sólido
  • Química
    • Química orgánica
      • Mecanismos de reacción
  • Ciencias tecnológicas
    • Ingeniería y tecnología químicas
      • Síntesis química
• Enlaces
  • Tesis en acceso abierto en: TDX
• Resumen

  • The transition-metal catalysed [2+2+2] cycloaddition reaction is a highly efficient synthetic tool that allows six-membered polysubstituted carbo- and heterocyclic derivatives to be obtained in an atom economy process. This doctoral thesis is based on methodological and mechanistic studies of the rhodium(I)-catalysed [2+2+2] cycloaddition reaction. In particular, the use of hemilabile S-stereogenic and P-stereogenic ligands for the rhodium-catalysed [2+2+2] cycloaddition is described. The activity of these new catalytic systems is evaluated in the cycloaddition of three alkynes and in the enantioselective cycloaddition of enediynes to obtain chiral cyclohexa-1,3-dienes. Moreover, the participation of Baylis-Hillman adducts as alkene moieties for the partially intramolecular [2+2+2] cycloaddition is described for the synthesis of a set of enantioenriched bicyclic cyclohexadienes featuring a quaternary stereogenic centre. Finally, the mechanistic study of the [2+2+2] cycloaddition of alkynes by electrospray ionization mass spectrometry and DFT calculations is performed.