Substrate-Controlled Mechanistic Switch Between Protodemetalation and Oxidative Addition in Rh-Catalyzed Carbometalation: A DFT Study

Key Points

• This study aims to explore the mechanistic pathways for the Rh(I)-catalyzed carbometalation of dihydropyridines and dihydroquinolines.
• DFT computational analysis
• Comparison of enzymatic pathways for dihydropyridines and dihydroquinolines
• Identification of transition states and intermediates
• Dihydropyridines show a preference for alkene insertion followed by protodemetalation
• Dihydroquinolines follow a different pathway involving oxidative addition
• Distinct mechanistic routes lead to divergent enantioselectivity for both substrates