An acid-promoted pseudocine substitution manifold of γ-aminocyclopentenone enables divergent access to polycyclic indole derivatives.

We demonstrated γ-aminocyclopentenones to be a suitable surrogate for reactive cyclopentadienone via a pseudocine -substitution manifold. This approach enabled its orchestrated annulation with "tailored" bis-nucleophiles and to furnish complex β,γ-annulated cyclopentanoids or indole-based polycyclic architectures. This strategy represents a generalized means for direct, regioselective and stereoselective β,γ-functionalization of monosubstituted or unsubstituted aminocyclopentenones.