Rhodium(III)‐Catalyzed Asymmetric Access to Spirocycles through C−H Activation and Axial‐to‐Central Chirality Transfer.

Axial‐to‐central chirality transfer is an important strategy to construct chiral centers, where the axially chiral reagents are mostly limited to atropomerically stable ones. Reported herein is a RhIII‐catalyzed enantioselective spiroannulative synthesis of nitrones. The coupling proceeds via C−H arylation to give an atropomerically metastable biaryl, followed by intramolecular dearomative trapping under oxidative conditions with high degree of chirality transfer. [ABSTRACT FROM AUTHOR]