<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Chiral trialkyl monodentate phosphine ligands (I) elaborated on the binepine scaffold are synthesized and applied to the Pd‐catalyzed intramolecular asymmetric α‐arylation of aldehydes as well as the intermolecular asymmetric γ‐arylation of α, β‐unsaturated aldehydes.</p> </abstract>