Computational and Experimental Insights into Asymmetric Rh‐Catalyzed Hydrocarboxylation with CO ₂

Abstract The asymmetric Rh‐catalyzed hydrocarboxylation of α,β‐unsaturated carbonyl compounds was originally developed by Mikami and co‐workers but gives only moderate enantiomeric excesses. In order to understand the factors controlling enantioselectivity propose novel ligands for this reaction, we have used computational experimental methods study with different bidentate ligands. analysis C−CO 2 bond formation transition states DFT shows a preference outer‐sphere CO insertion, where can undergo backside or frontside reaction nucleophile. two that prefer StackPhos t Bu‐BOX, display an intriguing stacking interaction between N‐heterocyclic ring ligand (imidazole oxazoline). Our results support computationally predicted low excesses highlight difficulty in developing highly selective version reaction.