Herein we describe the design and synthesis of a novel family of bifunctional, chiral bicyclo[2.2.1]heptadiene ligands bearing aryl and secondary amido groups, and demonstrate their usefulness in the RhI‐catalyzed enantioselective addition reaction of arylboronic acids to N‐diphenylphosphinyl (N‐DPP)‐protected aldimines. Unlike the analogous RhI‐catalysts comprising diene ligands substituted with aryl and carboxylic ester groups, or only with aryl groups, the addition reaction proceeded with high stereoselectivity. The protocol tolerated a range of N‐DPP‐aldimines and arylboronic acids, producing the desired optically active N‐DPP‐protected amines with yields between 31–99 % and with ee values up to 91–99 %. The synthetic utility of the method was demonstrated by the conversion of N‐DPP‐protected amine 3 ae into the antifungal agent, bifonazole (13).