Organocatalytic Atroposelective Formal Diels–Alder Desymmetrization of N‑Arylmaleimides

The atroposelective desymmetrization of N-arylmaleimides was realized by means of a primary amine catalyzed Diels–Alder reaction of enones. The chiral axis as new element of chirality is generated under the remote control of the catalyst that selectively drives the formal Diels–Alder reaction through an exclusive stereochemical outcome.