Application of Rh(I)/Bicyclo[2.2.1]heptadiene Catalysts to the Enantioselective Synthesis of Chiral Amines

The development of efficient synthetic methods for accessing enantioenriched α‐chiral amines is of great importance in the disciplines of medicinal and synthetic organic chemistry. Enantioselective Rh‐catalyzed 1,2‐addition reactions to activated imine derivatives are regarded as useful protocols for forming α‐chiral amines. This personal account outlines our efforts to develop chiral bicyclo[2.2.1]heptadiene ligands for Rh‐catalyzed asymmetric additions of various organoboron reagents to a wide range of imine derivatives. Transformations of the thus‐obtained adducts into known natural products or molecules of pharmaceutical importance serve to confirm their synthetic usefulness. The development of Rh‐catalysts comprising chiral bicyclo[2.2.1]heptadiene ligands in the asymmetric addition reactions of various organoboron reagents to aldimine derivatives for the preparation of α‐chiral amines is summarized.