Nickel-Catalyzed\nAtroposelective Reductive [2 + 4]\nAnnulation toward Synthesis of Axially Chiral Biaryls

Herein, we demonstrate the successful\napplication of reductive\n[2 + 4] annulation in the atroposelective de novo benzene ring formation.\nThis nickel-catalyzed reaction between β-substituted α-naphthylalkynes\nand a biselectrophile of C(sp<sup>2</sup>)–X type offers an\nefficient and convenient method to prepare highly enantioenriched\nC<sub>1</sub>-symmetric axially chiral biaryls containing two preinstalled\nfunctionalities. The coupling products can be used as versatile synthetic\nintermediates to access bidentate ligands or bifunctional organocatalysts,\nand their utility in asymmetric catalysis is also showcased in this\ncontext.