Abstract A series of chiral phosphine‐imine ligands were synthesized starting with α‐amino acids and examined for palladium‐catalyzed asymmetric addition of arylboronic acids to cyclic N‐sulfonyl imines. High catalytic activities (up to 99% yield) and high enantioselectivities (up to 98% ee) were achieved for cyclic N‐sulfonyl aldimines and ketimines with five and six‐membered ring structures. magnified image