Observation of an unexpected, Lewis acid promoted displacement of latent reactive g-amino group on cyclopentenone presented unparalleled opportunity for enone functionalization and annulations with indole derivatives, which is developed in the current study. Herein, a vast range of C3/Nindolyl enones and indole alkaloid-like compound were accessed in excellent yields (up to 99 %) and selectivity through a one-pot operation. The mechanism most likely involves an unprecedented trait of Piancatelli-type rearrangement where influence of the gem-diaryl group appeared crucial.

Site-selective ring-opening process of two different aziridine classes with hydroperoxide is described herein that provides access to various α-and β-amino and α-(imino)-peroxy compounds. This strainrelease-driven peroxide addition to aziridines represents an alternative approach for entries to biologically significant heteroatom substituted organic peroxides and complements existing methods in the field. The peroxide products obtained by this method displayed a different reactivity during peroxide-specific rearrangement processes promoted by either acid or base. Mechanistic studies and useful synthetic elaboration of the products have also been presented.

The present work demonstrates γ-aminocyclopentenones as suitable surrogate for reactive cyclopentadienone via pseudocine-substitution manifold which enables its orchestrated annulation with tailored bis-nucleophiles and furnish complex β,γ-annulated cyclopentanoids or indole-based polycyclic...