Nitrobutadienes as powerful benzannulating agents: An unprecedented easy access to rare nitroindoles

Abstract We report herein an original protocol to the indole nucleus, which could contribute to significantly expand the synthetic access to a heterocyclic moiety of undeniable paramount importance. The protocol consists in the construction of the benzene ring onto a pyrrole (benzannulation) starting from 2,3-dinitro-1,3-butadienes. This appealing, metal-free process characterized by high atom economy and mild reaction conditions allows to synthesize indoles possessing nitro group(s) on the benzene ring: a result which cannot be likewise easily obtained by exploiting most common pathways such as functionalization of a preformed indole or heteroannulation of a suitable benzene derivative. From a mechanistic point of view, a stepwise, ionic process is suggested by the identification of a pivot dihydroindole intermediate whose interception facilitates some selectivity in the preparation of different nitroindoles.