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.