An Aza-Piancatelli Templated Reaction Manifold of 4-Aminocyclopentenones Enables Access to Complex Carbocyclic Assemblies

Capitalizing on the propensity of 1, 2-amino group migration in γ-aminocyclopentenone with a suitable promoter, gem-diaryl equipped systems unfolded an unprecedented avenue for the Lewis acid promoted displacement of γ-aniline group with nucleophiles such as indole. Such transformation, besides providing a means for direct γ-functionalization of cyclopentenones, presented innumerable scope for β, γ-annulation. Various tailored indolo bis-nucleophiles were explored in the current study that rendered an array of indole alkaloid-like compounds in excellent yields and selectivity through one-pot operation. Analysis of collective experimental observation along with designed control experiments strongly suggested the possibility of a retro aza-Piancatelli rearrangement, which is hitherto unknown in the context. Such repertoire could find potential applications in the synthesis of complex assemblies from the Piancatelli rearrangement and related processes. 1. Introduction 2. Aza-Piancatelli rearrangement and related domino processes 3. An unprecedented aza-Piancatelli-templated strategy for polycyclic assemblies 4. Summary and Outlook