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.

Asymmetric intramolecular direct hydroarylation of α-ketoamides gives various types of optically active 3-substituted 3-hydroxy-2-oxindoles in high yields with complete regioselectivity and high enantioselectivities (84-98% ee). This is realized by the use of the cationic iridium complex [Ir(cod)₂](BAr(F)₄) and the chiral O-linked bidentate phosphoramidite (R,R)-Me-BIPAM.

A ruthenium-catalyzed asymmetric arylation of aliphatic aldehydes and α-ketoesters with arylboronic acids has been developed, giving chiral alkyl(aryl)methanols and α-hydroxy esters in good yields. The use of a chiral bidentate phosphoramidite ligand (Me-BIPAM) achieved excellent enantioselectivities.

An efficient and highlye nantioselective direct alkylation process of acetanilides with 2-norbornene using ab is(phosphoramidite) cationic Ir catalytic system (up to 99 % ee)h as been reported. This methodology allows the facile preparation of enantiomerically enriched exo-2-(bicyclo[2.2.1]heptan-2-yl)anilines,w hich can be readily transformed into otherfunctionalities.