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A novel dihydroazepine‐bridged BIPHEP phosphoramidite ligand with an amino acid moiety in the backbone was synthesized and evaluated in the Rh‐catalyzed asymmetric hydrogenation. The scorpion tail‐like amino acid backbone is capable of hydrogen bond formation and able to shift the rotamer composition of the biphenyl axis with the two scissor‐like arms. Pivaloyl‐l‐valine was studied as chiral selector...