Enantioselective Synthesis of Atropisomeric Biaryls by Pd‐Catalyzed Asymmetric Buchwald–Hartwig Amination

N−C Biaryl atropisomers are prevalent in natural products and bioactive drug molecules. However, the enantioselective synthesis of such molecules has not developed significantly. Particularly, the enantioselective synthesis of N−C biaryl atropisomers by stereoselective metal‐catalyzed aryl amination remains unprecedented. Herein, a Pd‐catalyzed cross‐coupling strategy is presented for the synthesis of N−C axially chiral biaryl molecules. A broad spectrum of N−C axially chiral compounds was obtained with excellent enantioselectivities (up to 99 % ee) and good yields (up to 98 %). The practicality of this reaction was validated in the synthesis of useful biological molecules. A Pd‐catalyzed enantioselective amination of amidines has been developed for the synthesis of N−C biaryl atropisomers. A wide range of benzimidazole derivatives containing N−C axial chirality can be conveniently constructed in excellent yields and enantioselectivities by intramolecular amination.