Hydroxyl-Directed Rh(III)-Catalyzed C–H Functionalization: Access to Benzo[<i>de</i>]chromenes

Abstract

A cascade oxidative annulation reaction of heterocyclic ketene aminals (HKAs) with internal alkynes catalyzed by [Cp*RhCl₂]₂ and oxidized by Cu(OAc)₂·H₂O was developed to efficiently synthesize highly functionalized benzo[<i>de</i>]chromene derivatives in good to excellent yields. The reaction proceeded by the sequential cleavage of C(sp²)-H/O-H and C(sp²)-H/C(sp²)-H bonds. These multicomponent cascade reactions were highly regioselective. In addition, all of the benzo[<i>de</i>]chromene products exhibited intense fluorescence emission in the solid state, and they demonstrated concentration-dependent quenching in the presence of Fe³⁺, indicating that these compounds could be used in the recognition of Fe³⁺.