Asymmetric Synthesis of Axially Chiral N, N‐1,2‐Pentatomic Heterobiaryl Diamines by an Organocatalytic Arylation Reaction

Abstract The utilization of axially chiral biaryl diamines has been widely acknowledged as highly advantageous structures for the advancement of chiral catalysts and ligands. This highlights their extensive range of applications in asymmetric catalysis and synthesis. Herein, we devised a direct arylation reactions of 5‐aminopyrazoles with azonaphthalenes, utilizing chiral phosphoric acid as the catalyst. This method delivers structurally novel atroposelective N, N‐1,2‐azole heteroaryl diamines with high yields (up to >98 %) and good to excellent enantiomeric ratios while exhibiting a wide range of substrate compatibility.