Nickel-Catalyzed Atroposelective Reductive [2 + 4] Annulation toward Synthesis of Axially Chiral Biaryls

Herein, we demonstrate the successful application of reductive [2 + 4] annulation in the atroposelective de novo benzene ring formation. This nickel-catalyzed reaction between β-substituted α-naphthylalkynes and a biselectrophile of C(sp2)–X type offers an efficient and convenient method to prepare highly enantioenriched C1-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.