Control of Multiple Stereogenic Elements in Diaryl Ethers

We report a chiral phosphoric acid (CPA)‐catalyzed desymmetrizing aminoacetalization strategy of proaxially chiral dialdehydes that enables the construction of diaryl ethers bearing both central and axial chirality. This organocatalytic atroposelective heteroannulation proceeds under mild conditions, tolerates a broad range of functional groups, and delivers highly enantioenriched products with excellent diastereoselectivity. Kinetic studies revealed a high diastereomerization barrier (141.4 kJ·mol −1 ) for representative products, indicating strong configurational stability. The synthetic utility of this method was further demonstrated through diverse postfunctionalizations, which proceeded without erosion of stereochemical integrity. This strategy provides a versatile and efficient entry to structurally complex, nonbiaryl atropisomers featuring multiple stereogenic elements, thereby expanding the accessible chemical space of axially chiral scaffolds for applications in catalysis, materials science, and medicinal chemistry.