Catalytic Atroposelective Construction of Diarylethers and Diarylamines

Axially chiral diarylethers and diarylamines show similar configurational stability and represent a distinct class of atropisomers containing two adjacent atropisomeric axes. These scaffolds are prevalent in various biologically active natural products and pharmaceuticals, making their catalytic preparation a hot topic of significant interest in synthetic and medicinal chemistry. The unique axial chirality of diarylethers and diarylamines arises from restricted rotation around C–O and C–N single bonds, leading to a pair of adjacent chiral axes. This Review systematically summarizes synthetic strategies, mechanistic insights, and applications of axially chiral diarylethers and diarylamines, with an emphasis on catalytic asymmetric processes. Catalytic asymmetric approaches enabled by biocatalysis, organocatalysis and transition-metal catalysis are highlighted, and the majority of the present methodologies include desymmetrization and kinetic resolution. By providing a comprehensive overview of the current advances and further perspectives, this Review could serve as a valuable guide for organic chemists, medicinal chemists, and materials chemists working on the syntheses and applications of axially chiral diarylethers and diarylamines.