Development of an Aza-Piancatelli-Templated Reaction Manifold from 4-Aminocyclopentenones: Access to Complex Carbocyclic Assemblies

Abstract

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 bisnucleophiles 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

Key words

Indoles - aza-Piancatelli rearrangement - annulation - bisnucleophiles - cyclopentenone

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