The Mechanism and Origin of Enantioselectivity in the Rhodium-Catalyzed Asymmetric Ring-Opening Reactions of Oxabicyclic Alkenes with Organoboronic Acids: A DFT Investigation

The mechanism and origins of enantio- and stereoselectivity in the asymmetric ring-opening (ARO) reactions of oxabicyclic alkenes with organoboronic acids catalyzed by rhodium/Josiphos has been examined at the B3LYP/defTZVP level of theory. The mechanism consists of four steps including transmetalation, carborhodation, β-oxygen elimination, and hydrolysis. Energetic discrimination in the chirality-imparting step arises from attractive C–H−π interactions between the transmetalated aryl group and the Josiphos ligand, as well as steric clashes between the Josiphos ligand and the oxabicyclic alkene. Computational results indicate that the rate-determining step is involved in the hydrolysis of the rhodium­(I) alkoxide from the ring-opened intermediate. In the overall catalytic cycle, the greatest free energy barrier is 23.4 kcal/mol, which supports that the Rh-catalyzed ARO reactions take place at mild reaction conditions, which is consistent with experimental observations.