Mechanism and Origins of Enantioselectivity of Cobalt-Catalyzed Intermolecular Hydroarylation/Cyclization of 1,6-Enynes with N-Pyridylindoles

Density functional theory calculations were per-formed to investigate the cobalt-catalyzed intermolecular hydro-arylation/cyclization of 1,6-enynes withN-pyridylindoles. Thecomputations reveal that the reaction begins with the oxidativecyclization of 1,6-enyne to afford thefive-membered cobaltacycle,from which the metal-assisted Sigma-bond metathesis/C-C reductiveelimination led to thefinal hydroarylation/cyclization product. Theinitial oxidative cyclization constitutes the rate-determining step of the overall reaction. The steric repulsion and pi middotmiddotmiddot pi interactionwere found to play a crucial role in dictating the experimentally observed enantioselectivity

Automated summary

Density functional theory calculations were used to investigate the cobalt-catalyzed intermolecular hydro-arylation/cyclization reaction. The computations revealed that the reaction proceeds through an oxidative cyclization of 1,6-enynes, followed by metal-assisted sigma-bond metathesis/reductive elimination, leading to the final hydroarylation/cyclization product. The steric repulsion and pi···pi interaction were found to be crucial in determining the observed enantioselectivity.