Rhodium‐Catalyzed <i>ortho</i>‐Olefination of Sterically Demanding Benzamides: Application to the Asymmetric Synthesis of Axially Chiral Benzamides
Ryo Yoshimura, Ken Tanaka
Abstract
Abstract 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.
Topics & Concepts
RhodiumSteric effectsAxial symmetryCatalysisChemistryCombinatorial chemistryOrganic chemistryMathematicsGeometryAxial and Atropisomeric Chirality SynthesisCatalytic C–H Functionalization MethodsSynthesis and Catalytic Reactions