Enantioselective Assembly of Aza-Heterocycles through Pd(II)-Catalyzed Annulations Initiated by the Activation of C‒H Bonds

Abstract

In this PhD thesis, we described our efforts towards the development of a series of enantioselective Pd(II)-catalyzed formal cycloadditions initiated by the activation of C–H bonds, using allenes as cycloaddition partners. These transformations allowed the asymmetric assembly of highly valuable aza- heterocyclic structures in a straightforward and sustainable manner through the activation of either C(sp²)−H or C(sp³)−H bonds. On the one hand, we have discovered a kinetic resolution of allylamine derivatives based on a (4+2) annulation, providing an efficient entry to enantioenriched tetrahydropyridines. On the other hand, we have designed and developed acetylated versions of NOBIN (NOBINAc) as new chiral ligands, which have allowed the asymmetric assembly of 3- and 2-benzazepine skeletons through (5+2) annulations.