We disclose herein an atroposelective synthesis of novel bridged biaryls containing medium‐sized rings via N‐heterocyclic carbene organocatalysis. The reaction starts with addition of the carbene catalyst to the aminophenol‐derived aldimine substrate. Subsequent oxidation and intramolecular desymmetrization lead to the formation of 1,3‐oxazepine‐containing bridged biaryls in good yields and excellent enantioselectivities. These novel bridged biaryl products can be readily transformed into chiral phosphite ligands. Preliminary density function theory calculations suggest that the origin of enantioselectivity arises from the more favorable frontier molecular orbital interactions in the transition state leading to the major product.

We disclose herein an atroposelective synthesis of novel bridged biaryls containing medium-sized rings via Nheterocyclic carbene organocatalysis. The reaction starts with addition of the carbene catalyst to the aminophenolderived aldimine substrate. Subsequent oxidation and intramolecular desymmetrization lead to the formation of 1,3oxazepine-containing bridged biaryls in good yields and excellent enantioselectivities. These novel bridged biaryl products can be readily transformed into chiral phosphite ligands. Preliminary density function theory calculations suggest that the origin of enantioselectivity arises from the more favorable frontier molecular orbital interactions in the transition state leading to the major product.