Biaryl atropisomers are of great importance in natural products, pharmaceuticals, and asymmteric synthesis. The efficient synthesis of these chiral scaffolds with full enantiocontrol and high diversity remains challenging. Reported herein is a Pd‐catalyzed atroposelective C−H allylation with tert‐leucine as an efficient catalytic chiral transient auxiliary. A wide range of enantioenriched biaryl aldehydes were prepared in synthetically useful yields with excellent enantioselectivity (up to >99 % ee) through β‐O elimination. The reaction could be carried out on a gram scale without erosion of the ee value. A variety of axially chiral carboxylic acids could be obtained with high enantiopurity. The resulting axially chiral biaryl aldehydes and carboxylic acids might be used in asymmetric synthesis as chiral ligands and/or organocatalysts. A Pd‐catalyzed atroposelective C−H allylation with allylic surrogates is reported. tert‐Leucine was identified as an efficient catalytic transient chiral auxiliary. A range of enantioenriched biaryls were prepared in synthetically useful yields with enantioselectivities up to >99 % ee through β‐O elimination. The reaction could be scaled up and the products could be further converted into enantiomerically pure axially chiral carboxylic acids.