Aminocatalytic Strategy for the Synthesis of Optically Active Benzothiophene Derivatives

A novel approach for the stereoselective synthesis of benzothiophene derivatives with a fused dihydropyran moiety is demonstrated. The reaction of 2‐alkylidenebenzothiophene‐3(2 H )‐ones with dienamines derived from α,β‐unsaturated aldehydes and chiral secondary amines proceeds according to the inverse‐electron‐demand hetero‐Diels–Alder pathway. The formation of the aromatic benzothiophene moiety is a driving force for the developed reaction cascade. Target products bearing three adjacent stereogenic centers are obtained in excellent yields and in a highly stereoselective manner.