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

Abstract

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.