Herein, we demonstrate the successful application of reductive [2 + 4] annulation in the atroposelective de novo benzene ring formation. This nickel-catalyzed reaction between βsubstituted α-naphthylalkynes and a biselectrophile of C(sp 2 )−X type offers an efficient and convenient method to prepare highly enantioenriched C 1 -symmetric axially chiral biaryls containing two preinstalled functionalities. The coupling products can be used as versatile synthetic intermediates to access bidentate ligands or bifunctional organocatalysts, and their utility in asymmetric catalysis is also showcased in this context.