Rhodium‐Catalyzed ortho ‐Olefination of Sterically Demanding Benzamides: Application to the Asymmetric Synthesis of Axially Chiral Benzamides

It has been established that an unsubstituted cyclopentadienyl rhodium(III) (CpRh III ) complex is a highly active catalyst for the aerobic oxidative ortho C−H bond olefination of sterically demanding ortho ‐substituted benzamides with alkenes. This catalysis was successfully applied to the diastereoselective synthesis of axially chiral N , N ‐dialkylbenzamides. The combination of the ruthenium(II)‐catalyzed enantioselective hydrogenation and the CpRh III ‐catalyzed diastereoselective ortho C−H bond olefination enabled the asymmetric synthesis of axially chiral N , N ‐dialkylbenzamide derivatives with high ee values.