Origins of regioselectivity in Ni-catalyzed hydrofunctionalization of alkenes via ligand-to-ligand hydrogen transfer mechanism.

The origins of regioselectivity in Ni-catalyzed alkene hydrofunctionalizations were computationally investigated by using energy decomposition analysis. The results indicate the Markovnikov selectivity with aryl-substituted alkenes is favored due to the stabilizing charge transfer effect, and the anti-Markovnikov selectivity with alkyl-substituted alkenes is favored because of the destabilizing Pauli repulsion effect.