Origins of Regioselectivity in CuH-Catalyzed Hydrofunctionalization of Alkenes

Factors controlling the regioselectivity in alkene hydrocupration were computationally investigated using energy decomposition analysis. The results demonstrate that the Markovnikov-selective hydrocupration with electronically activated mono-substituted olefins is mostly affected by the destabilizing Pauli repulsion, which is due to the electron delocalization effect. The anti-Markovnikov-selective hydrocupration with 1,1-dialkyl-substituted terminal olefins is dominated by the repulsive electrostatic interactions, which is because of the unequal pi electron distribution caused by the induction effect of alkyl substituents.

Automated summary

The factors controlling the regioselectivity in alkene hydrocupration were investigated computationally using energy decomposition analysis. It was found that the Markovnikov-selective hydrocupration with electronically activated mono-substituted olefins is mainly influenced by destabilizing Pauli repulsion due to the electron delocalization effect. On the other hand, the anti-Markovnikov-selective hydrocupration with 1,1-dialkyl-substituted terminal olefins is dominated by repulsive electrostatic interactions caused by the unequal pi electron distribution induced by alkyl substituents.