Cationic Iridium/S-Me-BIPAM-Catalyzed Direct Asymmetric Intermolecular Hydroarylation of Bicycloalkenes

Highly enantioselective cationic iridium‐catalyzed hydroarylation of bicycloalkenes, by carbonyl‐directed CH bond cleavage, was accomplished using a newly synthesized sulfur‐linked bis(phosphoramidite) ligand (S‐Me‐BIPAM). The reaction provides alkylated acetophenone or benzamide derivatives in moderate to excellent yields and good to excellent enantioselectivities. Notably, the hydroarylation reaction of 2‐norbornene with N,N‐dialkylbenzamide proceeds with excellent enantioselectivity (up to 99 % ee) and high selectivity for the mono‐ortho‐alkylation product. Linked up: Asymmetric intermolecular hydroarylation of bicycloalkenes by CH bond cleavage has been developed. The use of a chiral sulfur‐linked bis(phosphoramidite) ligand (L*) led to excellent enantioselectivity. Notably, the hydroarylation of 2‐norbornene with N,N‐dialkylbenzamide proceeds with high selectivity for the mono‐ortho‐alkylation product. DCE=1,2‐dichloroethane.