Asymmetric Dearomatic Diels–Alder Reactions of Diverse Heteroarenes via π‑System Activation

An asymmetric dearomatic Diels–Alder protocol for various heteroarenes, such as benzofuran, benzothiophene, or even furan, has been developed via π-system activation. This method involves in situ generation of formal trienamine species embedding a heteroaromatic moiety, and an array of chiral fused frameworks with high molecular complexity and skeletal diversity were efficiently constructed in good to excellent stereoselectivity by the catalysis of a cinchona-based primary amine.