Funcionalización selectiva de enlaces c(sp3)–h alifáticos usando amidas como grupos directores y sistemas reactivos basados en yodo hipervalente/yodo: formación de enlaces c–n mediante transferencia intramolecular de átomos de hidrógeno

• Autores: Dionisio José Rodríguez Sosa
• Directores de la Tesis: Concepcion del Carmen Gonzalez Martin (dir. tes.), Antonio Jesús Herrera González (codir. tes.), Francisco Cosme García (codir. tes.)
• Lectura: En la Universidad de La Laguna ( España ) en 2016
• Idioma: español
• Tribunal Calificador de la Tesis: Víctor Sotero Martín García (presid.), Victor Manuel Rayon Rico (secret.), Massimo Bietti (voc.)
• Materias:
  • Química
    • Química orgánica
      • Radicales libres
      • Compuestos heterocíclicos
      • Mecanismos de reacción
• Enlaces
  • Tesis en acceso abierto en: RIULL
• Resumen

  • Throughout this thesis it is described our research on the functionalization of unactivated C(sp3)-H bonds, mainly from methyl groups, in nonconstrained molecules, to create new C(sp3)-N and C(sp3)-Br bonds. They were conducted through 1,5 hydrogen atom transference to nitrogen centered radicals, generated by treatment with the reactive systems PhI(OAc)2/I2 or PhI(OAc)2/Br2 under irradiation of several precursors such as sulfonamides, cyclic sulfamates and cyclic sulfamides.

    All these precursors allowed the regio- and chemoselective synthesis of pyrrolidines, g-lactams and cyclic imines. The mechanisms of the functionalizations and the oxidation to imines were also investigated in order to improve the chemoselectivity. The evidence obtained let us propose a mechanistic pathway to explain the formation of each product.