上海科技大学知识管理系统

Axially chiral diaryl ethers represent a distinct class of atropisomers,characterized by a unique dual C─O axes system, which have been found in avariety of natural products, pharmaceuticals, and ligands. However, thecatalytic enantioselective synthesis of these atropoisomers poses significantchallenges, due to the difficulty in controlling both chiral C─O axes, and theirmore flexible conformations. Herein, an efficient protocol for catalyticenantioselective synthesis of axially chiral diaryl ethers is presented usingorganocatalyzed asymmetric Povarov reaction-enabled desymmetrization,followed by aromatizations. This method yields a wide range of novelquinoline-based diaryl ether atropoisomers in good yields and highenantioselectivities. Notably, various aromatization protocols are developed,resulting in a diverse set of polysubstituted quinoline-containing diaryl etheratropisomers. Thermal racemization studies suggested excellentconfigurational stabilities for these novel diaryl ether atropisomers (withracemization barriers up to 38.1 kcal mol−1 ). Moreover, this researchdemonstrates for the first time that diaryl ether atropisomers lacking the bulkyt-Bu group can still maintain a stable configuration, challenging the priorknowledge in the field. The fruitful derivatizations of the functional group-richchiral products further underscore the value of this method.