Herein, we report the use of a bromine atom as a masking group for the synthesis atropisomeric diarylamines via organocatalytic N ‐arylation of 7‐bromoindolines. The bromine atom acts as a bulky group to temporarily stabilize the configuration by steric hindrance. Upon unmasking, less sterically hindered diarylamines are obtained, with configurational stability potentially maintained through intramolecular hydrogen bonding. Moreover, the gram‐scale reaction and post‐modifications of the axially chiral diarylamines demonstrated the utility o...
