Computational mechanistic studies of transition metal catalyzed functionalizations of alkenes: nonintuitive enantioselectivity induction modes applied on contiguos stereocenter formation and difunctionalizations.
A variety of enantioselective functionalizations of alkenes using palladium oxazoline complexes has been reported in the last few years. The large majority of these processes can have their enantioselectivity rationalized by invoking repulsive steric interactions between the allylic hydrogens of the alkene and a bulky substituent at the oxazoline ligand. However, the origin of the enantioselectivity, in several other cases, could not be rationalized using the aforementioned model. Although these reactions are still regarded as exceptions, the understanding of their enantioselectivity induction mode can lead to a paradigm shift on the development of new alkene functionalization methodologies, with especially intriguing consequences on the creation of contiguous stereocenters and difunctionalizations. This project aims at the computational investigation and rationalization of these enantioselectivity induction modes directly corroborating with the development of new synthetic methodologies.
News published in Agência FAPESP Newsletter about the scholarship: